CN118126278A - Tall oil-based polyurethane synthetic leather and preparation method and application thereof - Google Patents
Tall oil-based polyurethane synthetic leather and preparation method and application thereof Download PDFInfo
- Publication number
- CN118126278A CN118126278A CN202410544218.7A CN202410544218A CN118126278A CN 118126278 A CN118126278 A CN 118126278A CN 202410544218 A CN202410544218 A CN 202410544218A CN 118126278 A CN118126278 A CN 118126278A
- Authority
- CN
- China
- Prior art keywords
- tall oil
- parts
- weight
- synthetic leather
- based polyurethane
- 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.)
- Granted
Links
- 239000003784 tall oil Substances 0.000 title claims abstract description 153
- 239000002649 leather substitute Substances 0.000 title claims abstract description 74
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 69
- 239000004814 polyurethane Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 60
- 229920005862 polyol Polymers 0.000 claims abstract description 59
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 46
- 239000000194 fatty acid Substances 0.000 claims abstract description 46
- 229930195729 fatty acid Natural products 0.000 claims abstract description 46
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000010985 leather Substances 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 229920005749 polyurethane resin Polymers 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000004902 Softening Agent Substances 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 208000035874 Excoriation Diseases 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- -1 compound polyol Chemical class 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Chemical class O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 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 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical class OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000007945 N-acyl ureas Chemical class 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention provides a tall oil-based polyurethane synthetic leather, a preparation method and application thereof, wherein the preparation raw materials of the tall oil-based polyurethane synthetic leather comprise tall oil-based polyol, isocyanate, a first catalyst, a flame retardant and a softener, and the preparation raw materials of the tall oil-based polyol comprise epoxidized tall oil fatty acid, small molecular alcohol and a second catalyst, and the preparation raw materials of the epoxidized tall oil fatty acid comprise tall oil fatty acid, acetic acid, ion exchange resin and oxidant; the tall oil-based polyol and the isocyanate are matched, and the preparation raw materials of the tall oil-based polyol are limited, so that the obtained polyurethane synthetic leather has excellent wear resistance, solvent resistance and flame retardance, and has the advantages of high mechanical strength, high peeling strength, soft hand feeling and low cost, and can be used as sheet leather or seat leather.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to tall oil-based polyurethane synthetic leather and a preparation method and application thereof.
Background
With the increasing concept of environmental protection and sustainable development, it is increasingly becoming appreciated that biobased materials are critical to the development of green recycling and decarbonization economics. At present, raw materials of fossil energy used in industry are not sustainable, while raw materials of natural resources have virtually unlimited reproducibility, and further in terms of sustainable development, bio-based raw materials are considered as a mode suitable for circular economy development, and also as a way of reducing carbon footprint.
Polyurethane resins are widely used in the preparation of high performance materials such as synthetic leather, foam, paint, elastomer, adhesives, sealants, and the like. The polyol prepared by taking vegetable oil as a raw material is used for replacing polyol based on petrochemical energy, and shows a more green and environment-friendly sustainable development direction. CN117362614A discloses a bio-based oligomer polyol and bio-based solvent-free polyurethane resin, wherein the bio-based oligomer polyol is prepared from 20-30 parts of bio-based polyether polyol, 30-90 parts of bio-based micromolecular dihydric alcohol, 100-150 parts of bio-based 2, 5-furandicarboxylic acid and 0.02-0.04 part of tetraisobutyl titanate according to parts by mass; the bio-based oligomer polyol structure contains furan and ester groups with high rigidity and ether groups with good low-temperature flexibility, and particularly, the existence of the furan structure ensures that the bio-based oligomer polyol structure is used in the bio-based solvent-free polyurethane in the subsequent process, so that the bio-based oligomer polyol has good low-temperature flexibility and mechanical properties; the component A and the component B prepared by the bio-based oligomer polyol are used for preparing the bio-based solvent-free polyurethane synthetic leather, and the bio-based solvent-free polyurethane synthetic leather has excellent peel strength, low Wen Qunao performance and yellowing resistance. CN115850645A discloses a high bio-based content aqueous polyurethane dispersion for synthetic leather and a preparation method thereof, wherein the aqueous polyurethane dispersion is prepared from the following components in parts by mass: 10.0-15.0 parts of bio-based isocyanate, 20.0-30.0 parts of bio-based polylactic acid polyol, 1.0-2.5 parts of bio-based chain extender, 0.5-1.0 parts of environment-friendly catalyst, 0.5-1.0 parts of bio-based antioxidant, 1.0-2.5 parts of neutralizer, 0.5-3.0 parts of post-chain extender and 75.0-100.0 parts of deionized water; the invention uses carboxyl in the side chain of the bio-based polylactic acid polyol as hydrophilic group, and adopts a self-emulsifying method to prepare the aqueous polyurethane dispersion liquid with high bio-based content.
It has been found that one of the most suitable starting materials for the preparation of bio-based materials is fatty acid, which is present in the plant in the form of triglycerides, and that crude tall oil contains fatty acids, rosin acids and other residues, and that distillation separation of crude rosin acids gives approximately 95% or more tall oil fatty acids, which have a high unsaturation content, which makes it relatively easy to convert carbon-carbon double bonds into more useful functional groups, and to introduce hydroxyl groups into unsaturated compounds, and further to produce the compound polyol necessary for polyurethane by polycondensation. Numerous researchers have now studied various methods of extracting polyols from vegetable oils, including but not limited to: epoxidation and ring opening of oxygen ring, hydroformylation and hydrogenation, ozonolysis, air oxidation, photochemical epoxidation, etc., but almost all published reports on synthetic polyols of vegetable oils have focused on the synthesis of polyols of low or medium functionality, resulting in poor solvent resistance, abrasion resistance and mechanical properties of polyurethane resins further prepared from the extracted vegetable oil polyols, and being difficult to use as sheet leather or seat leather.
Therefore, in view of the above technical problems, there is an urgent need to develop a tall oil-based polyurethane synthetic leather having excellent abrasion resistance, solvent resistance and mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide tall oil-based polyurethane synthetic leather, and a preparation method and application thereof, wherein the tall oil-based polyurethane synthetic leather has good wear resistance, flame retardance, solvent resistance and higher mechanical strength, can be used as sheet leather or seat leather, and can effectively solve the problems that the surface of the existing sheet leather or seat leather is easy to wear and is scratched after being rubbed by alcohol for many times.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a tall oil-based polyurethane synthetic leather, the tall oil-based polyurethane synthetic leather having a preparation raw material comprising a tall oil-based polyol, an isocyanate, a first catalyst, a flame retardant, and a softener;
The tall oil-based polyol is prepared from a feedstock comprising epoxidized tall oil fatty acid, a small molecule alcohol, and a second catalyst;
The preparation raw materials of the epoxidized tall oil fatty acid comprise tall oil fatty acid, acetic acid, ion exchange resin and oxidant.
Specifically, the tall oil-based polyurethane synthetic leather has excellent wear resistance, is not easy to scratch after being polluted and is not easy to corrode when being disinfected by alcohol, and meanwhile, the tall oil-based polyurethane synthetic leather has the advantages of high mechanical strength, excellent flame retardant property, soft hand feeling and low cost, and can be applied as sheet leather or seat leather.
Preferably, the tall oil-based polyurethane synthetic leather comprises the following raw materials in parts by weight:
60-70 parts by weight of tall oil based polyol;
25-35 parts of isocyanate;
0.001-0.004 parts by weight of a first catalyst;
0.5-2 parts by weight of a flame retardant;
and 0.5-2 parts by weight of a softening agent.
The content of the tall oil-based polyol in the raw material for preparing the tall oil-based polyurethane synthetic leather is 60-70 parts by weight, for example, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight or 70 parts by weight, etc.
The content of isocyanate in the raw materials for preparing the tall oil-based polyurethane synthetic leather is 25-35 parts by weight, for example, 25 parts by weight, 27 parts by weight, 29 parts by weight, 31 parts by weight, 33 parts by weight, 35 parts by weight or the like.
The content of the first catalyst in the raw material for preparing the tall oil-based polyurethane synthetic leather is 0.001-0.004 weight parts, for example, 0.001 weight parts, 0.002 weight parts, 0.003 weight parts, 0.004 weight parts, or the like.
The content of the flame retardant in the raw materials for preparing the tall oil-based polyurethane synthetic leather is 0.5-2 parts by weight, for example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight or 2 parts by weight and the like.
The content of the softener in the raw materials for preparing the tall oil-based polyurethane synthetic leather is 0.5-2 parts by weight, for example, 0.5 part by weight, 1 part by weight, 1.5 parts by weight or 2 parts by weight and the like.
Preferably, the tall oil based polyol has a hydroxyl number of 54 to 58 mg KOH/g, such as 54 mg KOH/g, 55 mg KOH/g, 56 mg KOH/g, 57 mg KOH/g, 58 mg KOH/g, or the like.
Preferably, the tall oil based polyol has an acid number of less than or equal to 5mg KOH/g, such as 5mg KOH/g, 4 mg KOH/g, 3 mg KOH/g, 2mg KOH/g, or 1 mg KOH/g, etc.; if the acid value of the tall oil-based polyol is more than 5mg KOH/g, the side reaction is more in the subsequent process of preparing the polyurethane synthetic leather, and the performance of the finally obtained synthetic leather is affected.
In the present invention, the specific kinds of the isocyanate, the first catalyst, the flame retardant and the softening agent are not particularly limited, and materials conventional in the art may be selected, but in order to provide the obtained tall oil-based polyurethane synthetic leather with the most excellent abrasion resistance, solvent resistance and mechanical properties, the following preferable limitations are made:
Preferably, the isocyanate comprises any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate or trimethylhexamethylene diisocyanate.
Preferably, the catalyst is preferably any one or a combination of at least two of stannous octoate, bismuth carboxylate or dibutyltin dilaurate.
Preferably, the flame retardant is any one or a combination of at least two of antimony trioxide, magnesium hydroxide, aluminum hydroxide or a phosphotriester.
Preferably, the softening agent is preferably any one or a combination of at least two of amino modified silicone oil, sodium stearyl sulfonate or sorbitan and octadecylamine.
Preferably, the tall oil-based polyol is prepared from the following raw materials in parts by weight:
45-53 parts by weight of epoxidized tall oil fatty acid;
48-52 parts by weight of small molecular alcohol;
and 0.02-0.08 parts by weight of a second catalyst.
Wherein the content of the epoxidized tall oil fatty acid in the preparation raw material of the tall oil-based polyol is 45 to 53 parts by weight, for example, 45 parts by weight, 47 parts by weight, 49 parts by weight, 51 parts by weight, 53 parts by weight or the like.
The content of the small molecular alcohol in the tall oil-based polyol preparation raw material is 48-52 parts by weight, for example, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight or 52 parts by weight, etc.
The content of the second catalyst in the tall oil-based polyol preparation raw material is 0.02 to 0.08 parts by weight, for example, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, or the like.
Preferably, the small molecule alcohol comprises any one or a combination of at least two of diethylene glycol, trimethylolpropane, diethanolamine or methylpropanediol.
Preferably, the second catalyst comprises lithium perchlorate.
Preferably, the preparation raw materials of the epoxidized tall oil fatty acid comprise the following components in parts by weight:
38-48 parts by weight of tall oil fatty acid;
6-10 parts by weight of acetic acid;
6-11 parts by weight of ion exchange resin;
34-43 parts of an oxidant.
The content of the tall oil fatty acid in the raw material for producing the epoxidized tall oil fatty acid is 38 to 48 parts by weight, for example, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, or the like.
The content of the acetic acid in the raw material for preparing the epoxidized tall oil fatty acid is 6 to 10 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, etc.
The content of the ion exchange resin in the preparation raw material of the epoxidized tall oil fatty acid is 6 to 11 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight or 11 parts by weight, and the like.
The content of the oxidizing agent in the raw material for preparing the epoxidized tall oil fatty acid is 34 to 43 parts by weight, for example, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 43 parts by weight or the like.
Preferably, the oxidant comprises 30-40% (e.g. 30%, 32%, 34%, 36%, 38% or 40% etc.) of hydrogen peroxide aqueous solution by mass percent.
Preferably, the ion exchange resin comprises an anion exchange resin and/or a cation exchange resin.
In a second aspect, the present invention provides a method for preparing tall oil based polyurethane synthetic leather according to the first aspect, the method comprising the steps of:
(1) Mixing tall oil fatty acid, acetic acid and ion exchange resin, adding an oxidant for reaction, and separating liquid to obtain epoxidized tall oil fatty acid;
(2) Mixing small molecular alcohol and a second catalyst, adding the epoxidized tall oil fatty acid obtained in the step (1) for reaction, and introducing nitrogen to purge to reduce the acid value to obtain tall oil-based polyol;
(3) Mixing the tall oil-based polyol obtained in the step (2), a first catalyst, a flame retardant and a softening agent, and adding isocyanate to react to obtain the tall oil-based polyurethane resin;
(4) And (3) coating the tall oil-based polyurethane resin obtained in the step (3) on a release film, and drying to obtain the tall oil-based polyurethane synthetic leather.
In the preparation method, the tall oil fatty acid in the step (1) is subjected to epoxidation reaction, so that epoxidized tall oil fatty acid is obtained; the epoxy groups in the epoxidized tall oil fatty acid in step (2) can react with the hydroxyl groups in the small molecule alcohol to form new hydroxyl groups, thereby improving the functionality of the tall oil-based polyol; in the step (3), reacting the obtained tall oil-based polyol with isocyanate to obtain polyurethane resin; and finally, coating the obtained polyurethane resin on a release film in the step (4) to obtain the tall oil-based polyurethane synthetic leather, wherein the release film is required to be removed when the tall oil-based polyurethane synthetic leather is used.
In the present invention, in order to optimize the comprehensive properties of the resulting tall oil-based polyurethane synthetic leather, it is preferable that the above step (1) specifically includes: mixing tall oil fatty acid, acetic acid and ion exchange resin under a constant temperature water bath of 30-40 ℃ (such as 30 ℃, 35 ℃ or 40 ℃), dropwise adding an oxidant with a temperature of 35-40 ℃ (such as 35 ℃, 36 ℃,37 ℃, 38 ℃,39 ℃ or 40 ℃), dropwise adding time of 30-60 min (such as 30min, 35 min, 40 min, 45min, 50 min, 55 min or 60 min), controlling the temperature to be lower than 60 ℃ (such as 59 ℃, 58 ℃, 57 ℃, 56 ℃ or 55 ℃), and the like), reacting for 6-10 hours (such as 6 h, 7 h, 8 h, 9 h or 10 h), pouring the reaction solution into a separating funnel, adding warm water with a temperature of 40-60 ℃ (such as 40 ℃, 45 ℃,50 ℃, 55 ℃, or 60 ℃), and the like, washing for 4-8 times (such as 4 times, 5 times, 6 times, 7 times or 8 times, and the like), and removing residual moisture by using a rotary vacuum evaporator to obtain red epoxidized tall oil fatty acid.
In the present invention, in order to optimize the comprehensive properties of the resulting tall oil-based polyurethane synthetic leather, it is preferable that the above step (2) specifically includes: mixing small molecular weight and a catalyst, heating to 110-130 ℃ (e.g. 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃), dropwise adding epoxidized tall oil fatty acid for 20-40 min (e.g. 20min, 25 min, 30min, 35 min or 40min, etc.), keeping the temperature and stirring for 1-3 h (e.g. 1h, 1.5 h, 2h, 2.5 h or 3 h, etc.), heating again to 160-200 ℃ (e.g. 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ etc.), reacting for 5-10 h (e.g. 5h, 6 h, 7 h, 8h, 9 h or 10 h, etc.), and introducing nitrogen to purge to reduce the acid value, thus obtaining the tall oil polyol.
Preferably, the mixing in the step (3) is performed under stirring, and more preferably under stirring at a rotation speed of 800 to 1000 rpm (for example, 800 rpm, 850 rpm, 900 rpm, 950 rpm, 1000 rpm, etc.).
Preferably, the mixing time in the step (3) is 5-10 min, for example, 5min, 6 min, 7 min, 8min, 9 min or 10min, etc.
Preferably, the reaction in step (3) is carried out under stirring, and more preferably under stirring at a rotation speed of 800 to 1000 rpm (for example, 800 rpm, 850 rpm, 900 rpm, 950 rpm, 1000 rpm, etc.).
Preferably, the reaction time in the step (3) is 15-30 s, for example 15 s, 17 s, 19 s, 21 s, 25 s or 30 s, etc.
Preferably, the thickness of the coating in step (4) is 1-2 mm, such as 1 mm, 1.3 mm, 1.6 mm, 1.9 mm or 2 mm, etc.
Preferably, the temperature of the drying and curing in the step (4) is 90-130 ℃, for example 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or the like.
In a third aspect, the present invention provides a use of the tall oil based polyurethane synthetic leather as described in the first aspect, said use comprising as a sheet leather or a seat leather.
Compared with the prior art, the invention has the following beneficial effects:
(1) The tall oil-based polyurethane synthetic leather provided by the invention has excellent wear resistance, and the problems of skin abrasion and abrasion are not easy to occur after the leather is rubbed for many times;
(2) The tall oil-based polyurethane synthetic leather provided by the invention also has excellent solvent resistance and flame retardance, is soft in hand feeling, and is not easy to corrode by organic solvents such as alcohol;
(3) The preparation method of the tall oil-based polyurethane synthetic leather provided by the invention has the advantages of simple process, low cost and energy consumption and good application prospect, and is suitable for being used as sheet leather or seat leather.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless otherwise indicated, all materials used in the following embodiments of the present invention are conventional in the art and are commercially available.
Example 1
The preparation method of the tall oil-based polyurethane synthetic leather comprises the following steps:
(1) Adding 38 parts by weight of tall oil fatty acid (Tianjin neutralization Chengtai chemical Co., ltd., NEUF 3033), 6 parts by weight of acetic acid and 6 parts by weight of anion exchange resin (Suzhou Tang Run environmental protection technology Co., ltd., D301) into a reaction bottle, connecting a mechanical stirrer, a thermocouple and a reflux condenser to the reaction bottle mouth, and then putting the reaction bottle into a constant-temperature water bath at 30 ℃ to stir uniformly; pouring 34 parts by weight of 30% hydrogen peroxide aqueous solution into a dropper, placing the dropper on a reaction bottle, starting to dropwise add the hydrogen peroxide aqueous solution when the temperature in the reaction bottle reaches 35 ℃, controlling the dropwise adding time to be 60 min, continuously stirring for reaction 6h after the hydrogen peroxide aqueous solution is dripped due to the fact that the reaction temperature in the reaction bottle is required to be controlled to be not higher than 60 ℃ during dropwise adding, pouring the reacted mixture into a separating funnel, washing with warm water at 40 ℃ for 8 times, and finally removing residual moisture in the mixture by using a rotary vacuum evaporator to obtain red epoxidized tall oil fatty acid;
(2) Adding 48 parts by weight of diethylene glycol and 0.08 part by weight of lithium perchlorate into a reaction bottle, connecting a condenser, a nitrogen purging pipe, a stirrer and a thermocouple at the opening of the reaction bottle, putting the reaction bottle into an oil bath, heating to 130 ℃, dripping 45 parts by weight of the epoxidized tall oil fatty acid obtained in the step (1), after dripping is completed in 20 min ℃, continuing to stir at 130 ℃ for 3 h, then raising the reaction temperature to 200 ℃ for continuous reaction for 10h, and introducing nitrogen purging to reduce the acid value to obtain tall oil-based polyol with the acid value below 5mg KOH/g and the hydroxyl value of about 56 mg KOH/g;
(3) Mixing 60 parts by weight of tall oil-based polyol obtained in the step (2), 0.001 part by weight of stannous octoate, 0.5 part by weight of antimony trioxide and 0.5 part by weight of amino-modified silicone oil (Stokes, silok-8525N) under the stirring condition with the rotating speed of 800 rpm for 10min, adding 25 parts by weight of isophorone diisocyanate, and reacting for 30s under the stirring condition of 800 rpm to obtain tall oil-based polyurethane resin;
(4) And (3) coating the tall oil-based polyurethane resin obtained in the step (3) on the surface of release paper, wherein the coating thickness is 1 mm, and then placing the release paper in a 90 ℃ oven for drying to obtain the tall oil-based polyurethane synthetic leather.
Example 2
The preparation method of the tall oil-based polyurethane synthetic leather comprises the following steps:
(1) Adding 43 parts by weight of tall oil fatty acid (Tianjin neutralization Cheng Tai chemical Co., ltd., NEUF 3033), 8 parts by weight of acetic acid and 8 parts by weight of cation exchange resin (Suzhou Tang Run environmental protection technology Co., ltd., 001 x 7) into a reaction bottle, connecting a mechanical stirrer, a thermocouple and a reflux condenser to the reaction bottle mouth, and then putting the reaction bottle into a constant-temperature water bath at 35 ℃ to stir uniformly; pouring 38 parts by weight of 35% hydrogen peroxide aqueous solution into a dropper, placing the dropper on a reaction bottle, starting to drop the hydrogen peroxide aqueous solution when the temperature in the reaction bottle reaches 37 ℃, controlling the drop time to be 45 min, increasing the reaction temperature in the reaction bottle during drop, keeping stirring for reaction 8 h after the hydrogen peroxide aqueous solution is dropped, pouring the reacted mixture into a separating funnel, washing for 6 times with warm water at 50 ℃, and finally removing residual moisture in the mixture by using a rotary vacuum evaporator to obtain red epoxidized tall oil fatty acid;
(2) Adding 50 parts by weight of trimethylolpropane and 0.05 part by weight of lithium perchlorate into a reaction bottle, connecting a condenser, a nitrogen purging pipe, a stirrer and a thermocouple at the opening of the reaction bottle, putting the reaction bottle into an oil bath, heating to 120 ℃, dripping 49 parts by weight of the epoxidized tall oil fatty acid obtained in the step (1), after dripping is completed in 30min, continuing to stir at 120 ℃ for 2h, then raising the reaction temperature to 200 ℃ to continue to react for 8 h, introducing nitrogen purging to reduce the acid value, and obtaining tall oil polyol with the acid value below 5mg KOH/g and the hydroxyl value of 56 mg KOH/g;
(3) Mixing 65 parts by weight of tall oil-based polyol obtained in the step (2), 0.002 part by weight of dibutyltin dilaurate, 1 part by weight of phosphotriester (Shandong China medicine biosciences Co., ltd., TCPP) and 1 part by weight of sodium stearyl sulfonate under the stirring condition with the rotating speed of 900 rpm for 8 min, adding 30 parts by weight of toluene diisocyanate, and reacting for 20 s under the stirring condition of 900 rpm to obtain tall oil-based polyurethane resin;
(4) And (3) coating the tall oil-based polyurethane resin obtained in the step (3) on the surface of release paper, wherein the coating thickness is 1.5 mm, and then placing the release paper in a 110 ℃ oven for drying to obtain the tall oil-based polyurethane synthetic leather.
Example 3
The preparation method of the tall oil-based polyurethane synthetic leather comprises the following steps:
(1) Adding 48 parts by weight of tall oil fatty acid (Tianjin neutralization Cheng Tai chemical Co., ltd., NEUF 3033), 10 parts by weight of acetic acid and 11 parts by weight of cation exchange resin (Suzhou Tang Run environmental protection technology Co., ltd., 001 x 7) into a reaction bottle, connecting a mechanical stirrer, a thermocouple and a reflux condenser to the reaction bottle mouth, and then putting the reaction bottle into a constant-temperature water bath at 40 ℃ to stir uniformly; pouring 43 parts by weight of hydrogen peroxide water solution with the concentration of 40% into a dropper, placing the dropper on a reaction bottle, starting to drop the hydrogen peroxide water solution when the temperature in the reaction bottle reaches 40 ℃, controlling the drop time to be 30min, increasing the reaction temperature in the reaction bottle when the drop is performed, continuously stirring for reaction for 10 h after the hydrogen peroxide water solution is dropped into the reaction bottle when the drop is performed, pouring the reacted mixture into a separating funnel, washing with warm water at 60 ℃ for 4 times, and finally removing residual moisture in the mixture by using a rotary vacuum evaporator to obtain red epoxidized tall oil fatty acid;
(2) Putting 52 parts by weight of diethanolamine and 0.02 part by weight of lithium perchlorate into a reaction bottle, connecting a condenser, a nitrogen purging pipe, a stirrer and a thermocouple at the opening of the reaction bottle, putting the reaction bottle into an oil bath, heating to 110 ℃, dripping 53 parts by weight of the epoxidized tall oil fatty acid obtained in the step (1), after dripping is completed in 40 min, continuing to stir at 110 ℃ for 1h, then raising the reaction temperature to 160 ℃ for continuous reaction for 5h, introducing nitrogen purging to reduce the acid value, and obtaining tall oil polyol with the acid value of below 5mg KOH/g and the hydroxyl value of about 56 mg KOH/g;
(3) Mixing 70 parts by weight of tall oil-based polyol obtained in the step (2), 0.004 parts by weight of bismuth carboxylate, 2 parts by weight of aluminum hydroxide and 2 parts by weight of sorbitan under the stirring condition with the rotating speed of 1000 rpm for 5min, adding 35 parts by weight of trimethylhexamethylene diisocyanate, and reacting 15 s under the stirring condition of 1000 rpm to obtain tall oil-based polyurethane resin;
(4) And (3) coating the tall oil-based polyurethane resin obtained in the step (3) on the surface of release paper, wherein the coating thickness is 2 mm, and then placing the release paper in a baking oven at 130 ℃ for baking to obtain the tall oil-based polyurethane synthetic leather.
Examples 4 to 5
A tall oil-based polyurethane synthetic leather is different from example 1 in that the mass fractions of aqueous hydrogen peroxide solutions are 20% (example 4) and 50% (example 5), respectively, and other substances, amounts and preparation methods are referred to in example 1.
Example 6
A tall oil-based polyurethane synthetic leather differs from example 1 in that the acid value of the tall oil-based polyol is 7 mg KOH/g, and other materials, amounts and preparation methods are described in example 1.
Examples 7 to 8
A tall oil-based polyurethane synthetic leather differs from example 1 in that the hydroxyl number of the tall oil-based polyol is 40 mg KOH/g (example 7) and 70 mg KOH/g (example 8), respectively, and other materials, amounts and preparation methods are referred to in example 1.
Comparative example 1
The preparation method of the polyurethane synthetic leather comprises the following steps:
(1) Mixing 60 parts by weight of petrochemical polyol PTMG-2000, 0.001 part by weight of stannous octoate, 0.5 part by weight of antimony trioxide and 0.5 part by weight of amino-modified silicone oil (Stokes, silok-8525N) under the stirring condition with the rotating speed of 800 rpm for 10min, adding 25 parts by weight of isophorone diisocyanate, and reacting for 30 s under the stirring condition of 800 rpm to obtain tall oil-based polyurethane resin;
(2) And (3) coating the tall oil-based polyurethane resin obtained in the step (1) on the surface of release paper, wherein the coating thickness is 1 mm, and then placing the release paper in a 90 ℃ oven for drying to obtain the polyurethane synthetic leather.
Comparative example 2
A polyurethane synthetic leather is different from example 1 in that antimony trioxide is not added, and other substances, amounts and preparation methods are referred to in example 1.
Comparative example 3
A polyurethane synthetic leather is different from example 1 in that amino-modified silicone oil is not added, and other substances, amounts and preparation methods are all referred to example 1.
Performance test:
(1) Wear resistance: the abrasion resistance times are tested by referring to the method provided by the standard GB/T21196-2007, and the test condition is r/H22 weight, 1 kg pressure;
(2) Peel strength: using a tensile machine, and testing according to a method provided by a standard GB/T3903.3-2011;
(3) Flame retardancy: the burn rate was tested with reference to the method provided by Standard FMVSS-302;
(4) Alcohol rub resistance: the polyurethane synthetic leather is fixed well by using a clamp, so that the surface of the polyurethane synthetic leather is smooth and free of bubbles, cracks and impurities, 75% alcohol is wetted by using medical gauze on the premise of 1 kg loads, the cleaning is performed back and forth, the speed is 30 times/min, the stroke is 50mm, whether the surface of the polyurethane synthetic leather is abraded or not is observed, if the surface is complete and free of abrasion, the surface is perfectly abraded slightly, but free of skin breakage, the surface is worse, the surface is severely abraded and the skin breakage is poor; the instrument used was produced by Dongguan Longtian instruments and equipment Co., ltd, model number LT803.
The polyurethane synthetic leather provided in examples 1 to 8 and comparative examples 1 to 3 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
(1) The tall oil-based polyurethane synthetic leather provided in examples 1-3 has wear resistance as high as 1113-1205 times, peel strength as high as 79-85N, burning rate of 13-16 mm/min and good alcohol wiping resistance test results, and the tall oil-based polyurethane synthetic leather provided in examples 1-3 has excellent wear resistance, solvent resistance and flame retardance and also has higher peel strength;
(2) In example 4, the mass percentage of the aqueous hydrogen peroxide solution is lower, so that partial tall oil fatty acid does not undergo epoxidation reaction, therefore, the functionality of the obtained tall oil-based polyol is lower than that of example 1, the formed net structure is less, further the abrasion resistance and alcohol resistance of the obtained synthetic leather are obviously poorer, and the flame retardance also deviates a little;
(3) In the embodiment 5, the hydrogen peroxide aqueous solution with higher mass percentage is used, and as the hydrogen peroxide aqueous solution with higher mass percentage is added into the reaction bottle in a dropwise manner, the temperature rises rapidly, so that local side reaction can occur, the purity of the finally obtained product is insufficient, the obtained polyurethane structure is not regular enough, and the peeling strength of the synthetic leather is low;
(4) In example 6, the acid value of the tall oil-based polyol is higher, and the excessive carboxyl groups react with isocyanate to generate meshed acyl urea which has good wear resistance and alcohol resistance, but the excessive meshed structure can reduce the peeling strength of the synthetic leather;
(5) In example 7, the hydroxyl value of the tall oil-based polyol is lower, so that the molecular weight of the tall oil-based polyol is higher, and the polyurethane resin prepared from the tall oil-based polyol with too high molecular weight is also higher in molecular weight, so that when the tall oil-based polyol is coated on the surface of release paper and put into an oven for foaming, the leather surface is quickly skinned, and the lower resin can be prevented from further foaming, so that the cell structure of the leather is irregular, and the peel strength is poor;
(6) In example 8, the tall oil-based polyol has a higher hydroxyl value, and the polyurethane resin obtained has a smaller molecular weight, so that the synthetic leather prepared from the polyurethane resin has poor wear resistance, peel strength and alcohol resistance;
(7) In comparative example 1, petrochemical polyol PTMG-2000 was used instead of tall oil-based polyol, and since PTMG-2000 did not have a good polyfunctional structure, polyurethane resin having a network structure could not be formed, and thus, abrasion resistance, alcohol resistance and flame retardant property were poor;
(8) In the comparative example 2, antimony trioxide is not added, and the obtained synthetic leather has poor flame retardant property and does not meet the requirements;
(9) The synthetic leather obtained in comparative example 3, which was not added with amino-modified silicone oil, had good basic physical properties, but had a feel significantly inferior to that of example 1, i.e., had no softness of example 1.
The applicant states that the present invention is described by way of the above examples as a tall oil based polyurethane synthetic leather and a method of making and using the same, but the present invention is not limited to, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A tall oil-based polyurethane synthetic leather, characterized in that the tall oil-based polyurethane synthetic leather is prepared from raw materials including tall oil-based polyol, isocyanate, a first catalyst, a flame retardant and a softener;
The tall oil-based polyol is prepared from a feedstock comprising epoxidized tall oil fatty acid, a small molecule alcohol, and a second catalyst;
The preparation raw materials of the epoxidized tall oil fatty acid comprise tall oil fatty acid, acetic acid, ion exchange resin and oxidant.
2. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the preparation raw materials of the tall oil-based polyurethane synthetic leather each independently comprise the following components in parts by weight:
60-70 parts by weight of tall oil based polyol;
25-35 parts of isocyanate;
0.001-0.004 parts by weight of a first catalyst;
0.5-2 parts by weight of a flame retardant;
And 0.5-2 parts by weight of a softening agent.
3. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the hydroxyl value of the tall oil-based polyol is 54-58 mg KOH/g, and the acid value is less than or equal to 5mg KOH/g.
4. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the tall oil-based polyol comprises the following raw materials in parts by weight:
45-53 parts by weight of epoxidized tall oil fatty acid;
48-52 parts by weight of small molecular alcohol;
and 0.02-0.08 parts by weight of a second catalyst.
5. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the small molecule alcohol includes any one or a combination of at least two of diethylene glycol, trimethylolpropane, diethanolamine, or methylpropanediol;
The second catalyst comprises lithium perchlorate.
6. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the preparation raw materials of the epoxidized tall oil fatty acid comprise the following components in parts by weight:
38-48 parts by weight of tall oil fatty acid;
6-10 parts by weight of acetic acid;
6-11 parts by weight of ion exchange resin;
34-43 parts of an oxidant.
7. The tall oil-based polyurethane synthetic leather according to claim 1, wherein the oxidant comprises 34-43% by mass of hydrogen peroxide aqueous solution.
8. A method for preparing tall oil-based polyurethane synthetic leather according to any one of claims 1to 7, characterized in that the method comprises the steps of:
(1) Mixing tall oil fatty acid, acetic acid and ion exchange resin, adding an oxidant for reaction, and separating liquid to obtain epoxidized tall oil fatty acid;
(2) Mixing small molecular alcohol and a second catalyst, adding the epoxidized tall oil fatty acid obtained in the step (1) for reaction, and introducing nitrogen to purge to reduce the acid value to obtain tall oil-based polyol;
(3) Mixing the tall oil-based polyol obtained in the step (2), a first catalyst, a flame retardant and a softening agent, and adding isocyanate to react to obtain the tall oil-based polyurethane resin;
(4) And (3) coating the tall oil-based polyurethane resin obtained in the step (3) on a release film, and drying to obtain the tall oil-based polyurethane synthetic leather.
9. The method according to claim 8, wherein the thickness of the coating in the step (4) is 1-2 mm, and the drying temperature is 90-130 ℃.
10. Use of tall oil-based polyurethane synthetic leather according to any one of claims 1 to 7, characterized in that the use comprises as sheet leather or seat leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410544218.7A CN118126278B (en) | 2024-05-06 | 2024-05-06 | Tall oil-based polyurethane synthetic leather and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410544218.7A CN118126278B (en) | 2024-05-06 | 2024-05-06 | Tall oil-based polyurethane synthetic leather and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118126278A true CN118126278A (en) | 2024-06-04 |
| CN118126278B CN118126278B (en) | 2024-07-12 |
Family
ID=91237923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410544218.7A Active CN118126278B (en) | 2024-05-06 | 2024-05-06 | Tall oil-based polyurethane synthetic leather and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118126278B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3211674A (en) * | 1961-08-22 | 1965-10-12 | Mobay Chemical Corp | Polyurethane foam from hydroxylated tall oil |
| WO1992000337A1 (en) * | 1990-06-27 | 1992-01-09 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous polyurethane dispersions, their production and their use in dressing leather |
| WO1992000336A1 (en) * | 1990-06-27 | 1992-01-09 | Henkel Kommanditgesellschaft Auf Aktien | Use of aqueous polyurethane dispersions in leather dressing |
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
| CN105622890A (en) * | 2016-03-01 | 2016-06-01 | 陕西科技大学 | Method for preparing tall oil water-based polyurethane |
| CN111842082A (en) * | 2020-07-28 | 2020-10-30 | 漳浦致远皮革有限公司 | Production method of antifouling folding-resistant leather |
| CN113527623A (en) * | 2021-07-30 | 2021-10-22 | 浙江华峰合成树脂有限公司 | Solvent-free polyurethane resin and preparation method and application thereof |
-
2024
- 2024-05-06 CN CN202410544218.7A patent/CN118126278B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3211674A (en) * | 1961-08-22 | 1965-10-12 | Mobay Chemical Corp | Polyurethane foam from hydroxylated tall oil |
| WO1992000337A1 (en) * | 1990-06-27 | 1992-01-09 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous polyurethane dispersions, their production and their use in dressing leather |
| WO1992000336A1 (en) * | 1990-06-27 | 1992-01-09 | Henkel Kommanditgesellschaft Auf Aktien | Use of aqueous polyurethane dispersions in leather dressing |
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
| CN105622890A (en) * | 2016-03-01 | 2016-06-01 | 陕西科技大学 | Method for preparing tall oil water-based polyurethane |
| CN111842082A (en) * | 2020-07-28 | 2020-10-30 | 漳浦致远皮革有限公司 | Production method of antifouling folding-resistant leather |
| CN113527623A (en) * | 2021-07-30 | 2021-10-22 | 浙江华峰合成树脂有限公司 | Solvent-free polyurethane resin and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 任龙芳;孙燕情;: "妥尔油改性水性聚氨酯的合成及性能研究", 聚氨酯工业, no. 06, 28 December 2016 (2016-12-28), pages 47 - 50 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118126278B (en) | 2024-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103305175B (en) | Environmental-friendly high-solid-content aqueous-polyurethane adhesive for shoes and preparation method thereof | |
| CN110804147A (en) | Bio-based waterborne polyurethane resin and application thereof | |
| CN107151302A (en) | One vegetable oil base flexible polyurethane foam and preparation method thereof | |
| CN112028801B (en) | Chain extender and preparation method and application thereof | |
| CN115197395A (en) | Aqueous polyurethane for impregnation of microfiber leather and preparation method and application thereof | |
| CN114736596B (en) | Quick-drying type single-component polyurethane waterproof coating and preparation method thereof | |
| CN114410201B (en) | Waterproof coating and preparation method thereof | |
| CN118126278B (en) | Tall oil-based polyurethane synthetic leather and preparation method and application thereof | |
| CN107151520A (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
| CN113929576A (en) | Preparation method of soybean oil polyalcohol | |
| CN111393627B (en) | Non-isocyanate polyurethane modified waterborne alkyd resin and preparation method thereof | |
| CN107151303A (en) | A kind of tung oil base RPUF and preparation method thereof | |
| CN114989380B (en) | Hydrolysis-resistant polyester polyurethane court material and preparation method thereof | |
| CN115058184B (en) | Water-based environment-friendly paint and preparation method thereof | |
| CN115260443A (en) | Waterborne polyurethane material and preparation method of waterborne polyurethane material applied to gloves | |
| CN114044872B (en) | Polyurethane resin for synthetic leather, water-absorbing moisture-permeable degradable synthetic leather and preparation method thereof | |
| CN112159509B (en) | Waterborne polyurethane and preparation method and application thereof | |
| Yuan et al. | Preparation and properties of tung oil-based polyurethane | |
| CN112409557B (en) | Vegetable oil-based polyurethane film and preparation thereof | |
| CN114106280A (en) | Aliphatic polyurethane resin and preparation method and application thereof | |
| CN114133529A (en) | Aromatic polyurethane resin and preparation method and application thereof | |
| CN114262565A (en) | Bi-component modified polyurethane waterproof coating and utilization method thereof | |
| CN107501520A (en) | A kind of antistatic treatment agent and preparation method thereof | |
| CN109627787B (en) | Preparation method of low-viscosity rubber oil | |
| CN111647348A (en) | Low-temperature ultraviolet curing powder coating containing biomass porous carbon and preparation method thereof |
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 |