CN114673013A - Modified TPU, modified TPU synthetic leather and preparation method thereof - Google Patents
Modified TPU, modified TPU synthetic leather and preparation method thereof Download PDFInfo
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- CN114673013A CN114673013A CN202210316729.4A CN202210316729A CN114673013A CN 114673013 A CN114673013 A CN 114673013A CN 202210316729 A CN202210316729 A CN 202210316729A CN 114673013 A CN114673013 A CN 114673013A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002649 leather substitute Substances 0.000 title claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000004744 fabric Substances 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- 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 abstract description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims description 22
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 13
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims 11
- 239000012790 adhesive layer Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 20
- 229920002050 silicone resin Polymers 0.000 abstract description 13
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical group [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 138
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 138
- 230000000052 comparative effect Effects 0.000 description 35
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ether diol Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical group CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/142—Hydrophobic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/145—Oleophobic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The application relates to the technical field of synthetic leather, and particularly discloses a modified TPU, a modified TPU synthetic leather and a preparation method thereof. The modified TPU comprises the following raw materials: polytetrahydrofuran ether glycol, isophorone diisocyanate, a modifier and a reaction auxiliary agent, wherein the modifier comprises tetrafluoropropanol, octafluoropentanol and a silane coupling agent; namely, introducing fluorine-silicon groups into TPU chain segments in a chain extending mode. The modified TPU synthetic leather comprises a base cloth layer, a bonding layer and a modified TPU layer, wherein the modified TPU layer comprises the following raw materials: silicone resin, modified TPU particles, other auxiliaries; the silicon resin is fused on the basis of the modified TPU particles, both the modified TPU particles and the silicon resin have excellent surface skin feel, hydrolysis resistance and stain resistance, and the finally prepared synthetic leather has excellent surface skin feel, hydrolysis resistance and stain resistance.
Description
Technical Field
The application relates to the technical field of synthetic leather, in particular to modified TPU, modified TPU synthetic leather and a preparation method thereof.
Background
The TPU is a thermoplastic polyurethane elastomer rubber for short, has the characteristics of high tension, high tensile force, toughness and aging resistance, can effectively reduce the pollution of chemical products to the environment due to the characteristic of recycling, and belongs to a mature environment-friendly material.
TPU has been widely used in the fields of medical hygiene, electronics, industry, sports, etc., and its properties are theoretically more suitable for the application in the field of synthetic leather. However, in the practical application process, because the synthetic leather product has higher requirements on skin feel, hydrolysis resistance and stain resistance of the surface of the material, the TPU material has obvious defects in the performance, so that the application of the TPU material in the field of synthetic leather is greatly limited.
Disclosure of Invention
In order to overcome the defects that the surface skin feel, hydrolysis resistance and stain resistance are poor when the TPU material is applied to the synthetic leather, the application provides the modified TPU, the modified TPU synthetic leather and the preparation method thereof.
In a first aspect, the present application provides a modified TPU, using the following technical scheme:
a modified TPU comprises the following raw materials in parts by mass: 80-110 parts of polytetrahydrofuran ether glycol, 35-60 parts of isophorone diisocyanate, 10-25 parts of a modifier and 10-20 parts of a reaction auxiliary agent, wherein the modifier is tetrafluoropropanol, octafluoropentanol and a silane coupling agent in a mass ratio of (2-4): (3-5): 1, in a mixture of the components.
By adopting the technical scheme, the polytetrahydrofuran ether diol and the isophorone diisocyanate are used as raw materials for synthesizing the TPU, the TPU prepolymer can be obtained under the action of a reaction auxiliary agent, and the TPU prepolymer is modified by the modifier, so that the surface skin feel and the hydrolysis resistance of the TPU prepolymer are improved to a certain extent, and meanwhile, the antifouling property is obviously improved.
Specifically, a group containing fluorine and silicon is introduced into the TPU prepolymer in a chain extension mode, and due to the fact that fluorine atoms are high in electronegativity and small in atom radius, the fluorine atoms have high electron binding performance, intermolecular interaction force can be effectively reduced, and the modified TPU has low surface energy. Meanwhile, the surface energy of the silane coupling agent is lower, and the migration capacity of the silicon element is higher than that of the fluorine element, so that the modified TPU has good hydrophobicity and lipophobicity; and the silane coupling agent enables a cross-linking structure formed by the system to enable the stability of the modified TPU to be better, and the surface skin feel, hydrolysis resistance and stain resistance of the prepared modified TPU are greatly improved.
In addition, the tetrafluoropropanol and the octafluoropentanol are selected as fluorine sources for chain extension, so that the introduction effect of fluorine-containing groups is good, the prepared modified TPU is not negatively affected, and the effect of the tetrafluoropropanol, the octafluoropentanol and the silane coupling agent compounded according to the proportion is good.
Preferably, the starting material further comprises a solution of ammonium dihydrogen phosphate.
By adopting the technical scheme, ammonium dihydrogen phosphate assists in solidifying the preliminarily modified TPU emulsion, so that the mechanical property and the flame retardant property of the TPU can be enhanced while the solidification effect is ensured. In addition, the modified TPU particles contain more zwitterions, the zwitterions are enriched on the surface of the TPU, and the zwitterions can effectively reduce the surface energy, the elastic modulus and the contact angle of the TPU, so that the modified TPU material has excellent antifouling performance.
In a second aspect, the present application provides a method for preparing a modified TPU, which adopts the following technical scheme:
a process for preparing a modified TPU comprising the steps of:
modification treatment: under the protection of nitrogen, mixing polytetrahydrofuran ether glycol, isophorone diisocyanate and a reaction auxiliary agent, reacting at 70-80 ℃ until NCO reaches a theoretical value, adding a modifier, continuing to react for 1-2 h, then cooling to 40-50 ℃, continuing to react, and shearing at a high speed to obtain a modified TPU emulsion;
and (3) post-treatment: and (3) carrying out curing, drying, crushing and granulating treatment on the modified TPU emulsion to obtain the finished modified TPU granules.
By adopting the technical scheme, the modifying agent is added in the process of synthesizing the TPU to modify the TPU, so that the group containing fluorine and silicon is introduced into the TPU prepolymer, and the surface skin feel, hydrolysis resistance and stain resistance of the modified TPU are effectively improved. In addition, the modified TPU emulsion after the curing and drying treatment is more stable and easy to store, and can be directly used as a TPU film, and the modified TPU granules after the crushing and granulating treatment are more suitable for preparing synthetic leather.
Preferably, in the post-treatment step, the polar solvent and the ammonium dihydrogen phosphate solution are mixed and stirred in advance to obtain a mixed solution for later use; and then adding the mixed solution into the modified TPU emulsion, and drying, crushing and granulating after the modified TPU emulsion is solidified to obtain the finished modified TPU granules.
By adopting the technical scheme, the polar solvent and the ammonium dihydrogen phosphate solution are mixed and stirred in advance, and the mixed solution is mixed with the modified TPU emulsion, so that the curing effect of the modified TPU emulsion is improved. Meanwhile, more zwitterions can be introduced into the modified TPU particles, so that the method has positive significance for improving the anti-fouling performance of the modified TPU material.
Preferably, in the post-treatment step, the temperature of the mixed solution is 40-80 ℃.
By adopting the technical scheme, the mixed solution at the temperature of 40-80 ℃ is beneficial to improving the curing effect of the modified TPU emulsion.
In a third aspect, the application provides a modified TPU synthetic leather, which adopts the following technical scheme:
the modified TPU synthetic leather comprises a base cloth layer, a bonding layer and a modified TPU layer, wherein the bonding layer is positioned between the base cloth layer and the modified TPU layer, and the modified TPU layer comprises the following raw materials in parts by mass: 20-30 parts of silicon resin, 50-65 parts of modified TPU particles and 2-10 parts of other auxiliary agents.
By adopting the technical scheme, the modified TPU particles have good surface skin feel, hydrolysis resistance and anti-fouling performance, and the modified TPU layer prepared by taking the modified TPU particles as the raw material is positioned on the outermost layer of the synthetic leather, so that the synthetic leather has good surface skin feel, hydrolysis resistance and anti-fouling performance. Meanwhile, as the silicon resin has smooth hand feeling, excellent hydrolysis resistance and self-antifouling performance, the surface skin feeling, hydrolysis resistance and antifouling performance of the modified TPU layer obtained by the blending technology of the silicon resin and the modified TPU particles are further improved.
Preferably, the raw materials of the bonding layer comprise the following components in parts by mass: 90-115 parts of water-based resin, 0.7-1 part of flatting agent, 0.03-0.05 part of defoaming agent, 4-6 parts of thickening agent and 8-10 parts of cross-linking agent.
By adopting the technical scheme, the adhesive prepared from the raw materials can better
Bonding the base fabric and the modified TPU layer, and has positive significance on the comprehensive performance of the synthetic leather.
In a fourth aspect, the application provides a preparation method of modified TPU synthetic leather, which adopts the following technical scheme: a preparation method of modified TPU synthetic leather comprises the following steps:
coating treatment: mixing and stirring the raw materials of the bonding layer in advance to obtain a binder; then transferring the binder to the surface of the base cloth, and baking for later use;
preparing a modified TPU layer: mixing and stirring the raw materials of the modified TPU layer to obtain a mixture, then extruding the mixture through an extruder to obtain a casting film, and forming the modified TPU layer for later use;
and (3) preparing a finished product: and (3) compounding and molding the modified TPU layer, the base cloth and the separable texture paper to obtain the finished synthetic leather.
By adopting the technical scheme, the raw materials of the modified TPU layer are mixed and extruded in the extruder, so that the silicone resin and the modified TPU particles are fully mixed, the bonding force between the silicone resin and the modified TPU particles can be effectively improved, the prepared modified TPU layer can effectively dissolve the advantages of the silicone resin and the modified TPU particles, and the prepared synthetic leather has excellent surface skin feel, hydrolysis resistance and stain resistance.
Preferably, in the step of preparing the modified TPU layer, the thickness of the prepared modified TPU layer is 0.2-0.4 mm.
By adopting the technical scheme, the modified TPU layer with the thickness of 0.2-0.4 mm has positive significance for improving the hand feeling of the synthetic leather.
In summary, the present application has the following beneficial effects:
1. according to the method, tetrafluoropropanol, octafluoropentanol and a silane coupling agent are added in the synthesis process of the TPU, so that a fluorine-silicon group is introduced into the TPU structure in a chain extending mode, the surface energy of the TPU is reduced, the modified TPU has good hydrophobicity and lipophobicity, and the modified TPU has good surface skin feel, hydrolysis resistance and stain resistance.
2. According to the preparation method, ammonium dihydrogen phosphate is added into the modified TPU emulsion to assist the emulsion in solidification, zwitterions are introduced into the modified TPU while the good solidification effect of the modified TPU emulsion is ensured, and the zwitterions have good surface energy, elastic modulus and contact angle which can effectively reduce the TPU, so that the modified TPU material has excellent antifouling performance.
3. Modified TPU particles and silicone resin are used as main raw materials of the synthetic leather, and the silicone resin is utilized to further improve the surface skin feel, hydrolysis resistance and stain resistance of the prepared synthetic leather on the basis that the modified TPU has good surface skin feel, hydrolysis resistance and stain resistance; and the modified TPU and the silicone resin have good binding capacity, so that the prepared synthetic leather is relatively stable.
Detailed Description
The raw materials in the preparation examples and the examples of the application can be obtained commercially, wherein the polytetrahydrofuran ether glycol is produced by Wuhana white pharmaceutical chemical company, and the product number is EF 234243;
isophorone diisocyanate is produced in sanderson chemical limited, Shandong, with a product number of 1021;
the methyl phenyl silicone resin is produced by Wuhan La Na white pharmaceutical chemical industry Co., Ltd, and has a product number of lnb-1519806;
the polyester type waterborne polyurethane resin is produced by Anhui femtosecond chemical industry Co., Ltd, and the product number is FS-1930C;
the polyurethane associative thickener is produced by Anhui femtosecond chemical industry Co., Ltd, and has the product number of N-140;
common TPU pellets are available from Suzhou Longoho plastification, Inc. under the 1180A designation.
The present application will be described in further detail with reference to examples.
Preparation of modified TPU
Preparation example 1
A modified TPU comprises the following raw materials in mass: 100kg of polytetrahydrofuran ether glycol, 50kg of isophorone diisocyanate, 15kg of modifier and 20kg of reaction auxiliary agent;
wherein the modifier is tetrafluoropropanol, octafluoropentanol and a silane coupling agent KH-550 according to the mass ratio of 3: 5: 1; the reaction auxiliary agent is a mixture consisting of 1, 4-butanediol, dimethylolbutyric acid, dibutyltin dilaurate, triethylamine and ethylenediamine according to the mass ratio of 1:1:1:1: 1.
The preparation method of the modified TPU comprises the following steps:
s1 modification treatment: under the protection of nitrogen, mixing and stirring polytetrahydrofuran ether diol and isophorone diisocyanate, reacting for 2 hours at the temperature of 70 ℃, then adding 1, 4-butanediol to continue reacting for 1 hour, and then adding dimethylolbutyric acid and dibutyltin dilaurate to continue reacting until NCO reaches a theoretical value; adding a modifier to continue reacting for 2 hours, then quickly cooling to 40 ℃, adding triethylamine to continue reacting for 30 min; after the mixture is cooled to 25 ℃, adding an ethylene diamine aqueous solution, and carrying out high-speed shearing emulsification for 15min to prepare a modified TPU emulsion;
and S2 post-processing: curing the modified TPU emulsion, dividing the cured modified TPU emulsion into blocks of 20cm by 2cm, and drying the blocks at 120 ℃ for 5 min; and airing the dried blocks at room temperature for 24h, and then carrying out crushing and granulating treatment to obtain finished modified TPU particles.
Preparation example 2
The difference between the preparation example and the preparation example 1 is that the raw material of the modified TPU further comprises an ammonium dihydrogen phosphate solution, and in the post-treatment step of S2, in the curing treatment process of the modified TPU, a polar solvent (deionized water) and the ammonium dihydrogen phosphate solution are mixed and stirred in advance to obtain a mixed solution with the molar concentration of ammonium dihydrogen phosphate being 2mol/L, and the mixed solution is heated to 50 ℃ for later use while keeping stirring; and then adding the mixed solution into the modified TPU emulsion, mixing and stirring for 3h at the stirring speed of 1000rpm, and drying, crushing and granulating after the modified TPU emulsion is solidified to obtain the finished modified TPU granules.
Preparation example 3
This preparation example differs from preparation example 2 in that the ammonium dihydrogen phosphate solution was replaced with an equal amount of an ammonium bicarbonate solution of equal concentration.
Comparative preparation example 1
This comparative preparation example differs from preparation example 1 in that the modifier is a mixture of tetrafluoropropanol and a silane coupling agent KH-550 in a mass ratio of 3: 1.
Comparative preparation example 2
This comparative preparation example differs from preparation example 1 in that the modifier is a mixture of octafluoropentanol and a silane coupling agent KH-550 in a mass ratio of 5: 1.
Comparative preparation example 3
This comparative preparation differs from preparation 1 in that the modifier is a mixture of tetrafluoropropanol and octafluoropentanol in a mass ratio of 3: 5.
Comparative preparation example 4
This comparative preparation differs from preparation 1 in that no modifier is added.
Examples
Example 1
A modified TPU synthetic leather comprises a base cloth layer, a bonding layer and a modified TPU layer, wherein the bonding layer is positioned between the base cloth layer and the modified TPU layer; the raw materials of the modified TPU layer comprise the following components in mass: 20kg of silicone resin, 60kg of modified TPU particles and 6kg of other auxiliary agents; the raw materials of the bonding layer comprise the following components by mass: 100kg of water-based resin, 0.8kg of flatting agent, 0.05kg of defoaming agent, 4kg of thickening agent and 10kg of crosslinking agent;
wherein the modified TPU particles are prepared as described in preparation example 1;
the other auxiliary agents comprise 2.4kg of stabilizing agent, 3.2kg of plasticizer and 0.4kg of flame retardant, the stabilizing agent is dibutyltin dilaurate, the plasticizer is dioctyl terephthalate, and the flame retardant is tricresyl phosphate;
the silicone resin is methyl phenyl silicone resin;
the water-based resin is polyester type water-based polyurethane resin;
the leveling agent is an organic silicon leveling agent;
the cross-linking agent is a closed water-based isocyanate cross-linking agent;
the thickener is polyurethane associative thickener;
the base cloth layer is the layer that leather base cloth, one of looped fabric, woven fabric, non-woven fabrics formed, and this embodiment base cloth layer is the layer that the leather base cloth formed.
The preparation method of the modified TPU synthetic leather comprises the following steps:
pretreatment of A1 base cloth: selecting a flat and intact base cloth, cleaning and drying for later use;
a2 coating treatment: mixing and stirring the raw materials of the bonding layer in advance to obtain a binder; then, transferring the binder to the surface of the base cloth by adopting a printing processing technology, and baking for 1min at the temperature of 130-140 ℃, wherein the running speed reaches 25-29 m/min;
preparation of A3 modified TPU layer: mixing and stirring the raw materials of the modified TPU layer at the stirring speed of 1200rpm to obtain a mixture, extruding the mixture by an extruder to obtain a casting film with the thickness of 0.2-0.4 mm, and forming the modified TPU layer for later use;
preparation of A4 finished product: and (3) compounding and molding the modified TPU layer, the base cloth and the separable texture paper (TPX release paper), namely, entering an inspection program after molding, cutting, packaging and marking according to the requirements of customers after the inspection is qualified, and thus obtaining the finished synthetic leather.
Example 2
This example differs from example 1 in that modified TPU granules were prepared for preparation example 2.
Example 3
This example differs from example 1 in that modified TPU granules were prepared for preparation example 3.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that no silicone resin is added, the complement is made up with an equal amount of modified TPU particles, and modified TPU particles are prepared as in preparation example 1.
Comparative example 2
This comparative example differs from example 1 in that the modified TPU granules are replaced by equal amounts of ordinary TPU granules.
Comparative example 3
This comparative example differs from example 1 in that modified TPU granules were prepared for comparative preparation example 1.
Comparative example 4
This comparative example differs from example 1 in that modified TPU pellets were prepared for comparative preparation example 2.
Comparative example 5
This comparative example differs from example 1 in that modified TPU pellets were prepared for comparative preparation example 3.
Comparative example 6
This comparative example differs from example 1 in that modified TPU pellets were prepared for comparative preparation example 4.
Comparative example 7
The comparative example differs from example 1 in that the modified TPU pellets were produced by melt extrusion of ordinary TPU pellets and the modifier in an extruder, the mass ratio of ordinary TPU pellets to modifier was 10:1, and the components of the modifier and the mass ratio of the components were unchanged.
Comparative example 8
This comparative example differs from example 1 in that the silicone resin and modified TPU particles are replaced with equal amounts of ordinary TPU particles.
Performance test
Detection method/test method
Subjective surface skin feel test: 100 volunteers with normal sense are selected, the surface skin feel test is carried out on the synthetic leather finished products prepared in the examples 1-3 and the comparative examples 1-8 respectively, the scores are carried out according to the score of 100, and the average score is calculated.
And (3) hydrolysis resistance testing: the synthetic leather finished products prepared in the examples 1-3 and the comparative examples 1-8 are tested according to the test method of constant temperature, constant humidity and hydrolysis resistance method (A method) in QB/T4671-.
And (3) pollution resistance performance test: the finished synthetic leather products obtained in examples 1 to 3 and comparative examples 1 to 8 were tested with reference to the test method in QB/T5070-.
TABLE 1 test data sheet
The detection data of the detection data table in the table 1 are combined with the detection results of the example 1 and the comparative example 8, so that the surface skin feel, hydrolysis resistance and stain resistance of the synthetic leather in the example 1 are obviously superior to those of the synthetic leather in the comparative example 8, and the introduction of the fluorine-silicon group in a chain extending manner can effectively reduce the surface energy of the modified TPU, so that the modified TPU has good hydrophobicity and lipophobia; and the silane coupling agent enables a cross-linked structure formed by the system to enable the stability of the modified TPU to be better, and the surface skin feeling, hydrolysis resistance and stain resistance of the prepared modified TPU are greatly improved. Namely, the modified TPU particles can be applied to synthetic leather to effectively improve the performance of the synthetic leather.
According to the detection results of the embodiments 1 to 3, in the curing process of the modified TPU emulsion, ammonium dihydrogen phosphate is introduced into the system, so that zwitterions in the system can be effectively increased, and the zwitterions can further improve the stain resistance of the modified TPU by reducing the surface energy, the elastic modulus and the contact angle of the TPU. And from the test results, the introduction of the zwitterion has a certain improvement effect on the skin feeling of the surface, and the improvement effect of the ammonium bicarbonate is not obvious, and the zwitterion introduced by the ammonium dihydrogen phosphate is high in quantity or is more stable.
Combining the test results of example 1 and comparative example 7, it is known that, the tetrafluoropropanol, octafluoropentanol and silane coupling agent are directly blended with the common TPU particles without introducing the fluorosilicone group in a chain extension manner, which may not improve the skin feel, hydrolysis resistance and stain resistance of the TPU surface and may have some negative effects.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A modified TPU, characterized by: the composite material comprises the following raw materials in parts by mass: 80-110 parts of polytetrahydrofuran ether glycol, 35-60 parts of isophorone diisocyanate, 10-25 parts of a modifier and 10-20 parts of a reaction auxiliary agent, wherein the modifier is tetrafluoropropanol, octafluoropentanol and a silane coupling agent in a mass ratio of (2-4): (3-5): 1, in a mixture of the components.
2. A modified TPU as set forth in claim 1 wherein: the raw material also comprises ammonium dihydrogen phosphate solution.
3. The process for preparing a modified TPU according to any of claims 1 to 2, characterized in that: the method comprises the following steps:
modification treatment: under the protection of nitrogen, mixing polytetrahydrofuran ether glycol, isophorone diisocyanate and a reaction auxiliary agent, reacting at 70-80 ℃ until NCO reaches a theoretical value, adding a modifier, continuing to react for 1-2 h, then cooling to 40-50 ℃, continuing to react, and shearing at a high speed to obtain a modified TPU emulsion;
and (3) post-treatment: and (3) carrying out curing, drying, crushing and granulating treatment on the modified TPU emulsion to obtain the finished modified TPU granules.
4. A process for preparing a modified TPU as set forth in claim 3 wherein: in the post-treatment step, the polar solvent and the ammonium dihydrogen phosphate solution are mixed and stirred in advance to obtain a mixed solution for later use; and then adding the mixed solution into the modified TPU emulsion, and drying, crushing and granulating after the modified TPU emulsion is solidified to obtain the finished modified TPU granules.
5. A process for preparing a modified TPU according to claim 4, characterized in that: in the post-treatment step, the temperature of the mixed solution is 40-80 ℃.
6. A modified TPU synthetic leather as set forth in claim 5, characterized in that: the adhesive layer is positioned between the base cloth layer and the modified TPU layer, and the modified TPU layer comprises the following raw materials in parts by mass: 20-30 parts of silicon resin, 50-65 parts of modified TPU particles and 2-10 parts of other auxiliary agents.
7. A modified TPU synthetic leather as set forth in claim 6, characterized in that: the bonding layer comprises the following raw materials in parts by mass: 90-115 parts of water-based resin, 0.7-1 part of flatting agent, 0.03-0.05 part of defoaming agent, 4-6 parts of thickening agent and 8-10 parts of cross-linking agent.
8. The preparation method of the modified TPU synthetic leather according to claim 7, which is characterized in that: the method comprises the following steps:
coating treatment: mixing and stirring the raw materials of the bonding layer in advance to obtain a binder; then transferring the binder to the surface of the base cloth, and baking for later use;
preparing a modified TPU layer: mixing and stirring the raw materials of the modified TPU layer to obtain a mixture, then extruding the mixture through an extruder to obtain a casting film, and forming the modified TPU layer for later use;
and (3) preparing a finished product: and (3) compounding and molding the modified TPU layer, the base cloth and the separable texture paper to obtain the finished synthetic leather.
9. The preparation method of the modified TPU synthetic leather according to claim 8, wherein the preparation method comprises the following steps: in the preparation step of the modified TPU layer, the thickness of the prepared modified TPU layer is 0.2-0.4 mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116199979A (en) * | 2023-01-10 | 2023-06-02 | 苏州硕宏高分子材料有限公司 | Pre-dispersed rubber accelerator and rubber prepared from same |
| CN116199979B (en) * | 2023-01-10 | 2024-05-17 | 苏州硕宏高分子材料有限公司 | Pre-dispersed rubber accelerator and rubber prepared from same |
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| CN105619558A (en) * | 2016-03-01 | 2016-06-01 | 山东农业大学 | Preparation method of organic-inorganic hybrid super-hydrophobic and oleophobic wood modifier with mold-proof, sterilization, anti-flaming and weather-proof properties |
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| CN105619558A (en) * | 2016-03-01 | 2016-06-01 | 山东农业大学 | Preparation method of organic-inorganic hybrid super-hydrophobic and oleophobic wood modifier with mold-proof, sterilization, anti-flaming and weather-proof properties |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116199979A (en) * | 2023-01-10 | 2023-06-02 | 苏州硕宏高分子材料有限公司 | Pre-dispersed rubber accelerator and rubber prepared from same |
| CN116199979B (en) * | 2023-01-10 | 2024-05-17 | 苏州硕宏高分子材料有限公司 | Pre-dispersed rubber accelerator and rubber prepared from same |
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