CN111206434A - Antibacterial wear-resistant synthetic leather and preparation method thereof - Google Patents
Antibacterial wear-resistant synthetic leather and preparation method thereof Download PDFInfo
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- CN111206434A CN111206434A CN202010101883.0A CN202010101883A CN111206434A CN 111206434 A CN111206434 A CN 111206434A CN 202010101883 A CN202010101883 A CN 202010101883A CN 111206434 A CN111206434 A CN 111206434A
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 46
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims abstract description 7
- TZEMBFLDHOUKNI-UHFFFAOYSA-N (2-amino-1,3-thiazol-5-yl)methanol Chemical compound NC1=NC=C(CO)S1 TZEMBFLDHOUKNI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims 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 description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 238000007792 addition Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 150000003863 ammonium salts Chemical group 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 abstract description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 239000010985 leather Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 241000208181 Pelargonium Species 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 functional group quaternary ammonium salt Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3874—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing heterocyclic rings having at least one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an antibacterial wear-resistant synthetic leather and a preparation method thereof, wherein the synthetic leather is prepared from modified polyurethane resin by a wet manufacturing process, firstly, a block modifier is researched and prepared, firstly, 2-amino-5- (hydroxymethyl) thiazole and N, N' -1, 3-phenylene bismaleimide are taken as raw materials, nucleophilic addition reaction is carried out on amino and carbon-carbon double bonds under an acidic condition to obtain an intermediate A, then the intermediate A reacts with dimethyl sulfate to obtain a block modifier B containing biquaternary ammonium salt, the block modifier B is added into the preparation of polyurethane to carry out block polymerization reaction, so that the physical properties of the polyurethane are changed, and the prepared synthetic leather has good antibacterial property and wear resistance.
Description
Technical Field
The invention belongs to the technical field of synthetic leather, and particularly relates to antibacterial wear-resistant synthetic leather and a preparation method thereof.
Background
The polyurethane synthetic leather has the excellent characteristics of soft and natural luster, soft hand feeling, strong real leather feeling, deflection resistance, aging resistance and the like, also has the advantages of good cold resistance, ventilation, washability, convenient processing, low price and the like, is the most ideal substitute of natural leather, and is widely applied to the industries of clothing, shoemaking, cases, furniture and the like. Along with the high-speed development of the synthetic leather industry, the quality requirement of polyurethane resin for synthetic leather is higher and higher, in the processing process of polyurethane products, the performance index of the polyurethane synthetic leather can be improved by adding different types of functional additives, but the defects that the additives are difficult to mix uniformly, additive molecules are easy to lose efficacy and overflow in long-term use, the additives have specific application fields and are matched with resin and the like exist.
The synthetic leather product is not easy to wash, bacteria are easy to breed if the synthetic leather product is placed after being worn, a specific leather cleaning agent needs to be regularly adopted for cleaning and maintenance, and how to improve the wear resistance and the antibacterial property of the synthetic leather has important significance for market development of the leather product.
Disclosure of Invention
The invention aims to provide antibacterial wear-resistant synthetic leather and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an antibacterial wear-resistant synthetic leather is prepared from modified polyurethane resin by a wet manufacturing process.
A preparation method of antibacterial wear-resistant synthetic leather specifically comprises the following steps:
first step, preparation of Block modifier
S1, adding 2.3-2.5mol of 2-amino-5- (hydroxymethyl) thiazole, 20-25g of acid catalyst and 4-6L of solvent acetone into a reaction kettle, heating to 60-65 ℃ while stirring, dividing into 5 batches equally, adding 1mol of N, N' -1, 3-phenylene bismaleimide, keeping the temperature and continuing stirring for 2.5-3h after the addition is finished, pouring the reaction solution into 2L of absolute ethyl alcohol after the reaction is finished, standing for 1h, filtering, washing for 3-5 times by using the absolute ethyl alcohol, and drying in vacuum to obtain an intermediate A;
s2, adding the intermediate A prepared in the step S1 and 3-4L of solvent into a reaction kettle, heating to 70-80 ℃ while stirring, dropwise adding 2.1-2.3mol of dimethyl sulfate, continuing to perform heat preservation reaction for 3.5-4 hours after dropwise adding, removing the solvent and unreacted dimethyl sulfate by reduced pressure distillation after the reaction is finished, and washing a crude product for 3-5 times by anhydrous ether to obtain a block modifier B;
second step, preparation of modified polyurethane resin
Adding dehydrated polypropylene glycol into a reaction kettle, adding a dried block modifier B, a chain extender, a catalyst and a solvent DMF, heating to 60-65 ℃, adding isophorone diisocyanate into the reaction kettle, heating to 80-85 ℃, and carrying out heat preservation reaction for 4-5 hours to obtain modified polyurethane resin;
and thirdly, penetrating the modified polyurethane resin into the non-woven fabric by adopting a wet manufacturing process to obtain the antibacterial wear-resistant synthetic leather.
Further, in step S1, the acid catalyst is p-toluenesulfonic acid.
Further, in step S1, N, N' -1, 3-phenylenebismaleimide was added in batches at intervals of 30 min.
Further, in step S2, the solvent is 35 to 40% ethanol water.
Further, in the second step, the mass ratio of the isophorone diisocyanate to the polyester polyol to the block modifier B to the chain extender to the catalyst is 45-50: 130-150:20-30:2-4:0.03.
Further, in the second step, the polyester polyol is PPG 2000.
Further, in the second step, the chain extender is pentaerythritol.
Further, in the second step, the catalyst is dibutyltin dilaurate.
Further, in the second step, the liquid-mass ratio of the solvent DMF to isophorone diisocyanate was 10ml:1 g.
The invention has the beneficial effects that:
the invention provides antibacterial wear-resistant synthetic leather and a preparation method thereof, wherein a block modifier is firstly researched and prepared, firstly, 2-amino-5- (hydroxymethyl) thiazole and N, N' -1, 3-phenylene bismaleimide are taken as raw materials, amino and carbon-carbon double bond are subjected to nucleophilic addition reaction under an acidic condition to obtain an intermediate A, then the intermediate A is reacted with dimethyl sulfate to obtain a biquaternary ammonium salt-containing block modifier B, and the biquaternary ammonium salt-containing block modifier B is added into the preparation of polyurethane to perform block polymerization reaction;
the block modifier B contains an antibacterial functional group quaternary ammonium salt and a thiazole ring, a dual antibacterial functional mechanism can inhibit various bacteria and mold, and the antibacterial functional group B is introduced into the synthetic leather in a chemical bond mode, has good scrubbing resistance, and can maintain the antibacterial property of the synthetic leather for a long time even if the synthetic leather is washed by a long-term detergent;
the block modifier B has a larger molecular structure and contains bismaleimide, so that the molecular weight of polyurethane resin is greatly improved, the crosslinking degree of polyurethane is greatly improved under the condition of pentaerythritol chain extender containing four hydroxyl groups, and synthetic leather made of the modified polyurethane resin has better wear resistance.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction scheme for preparing a block modifier according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, the preparation of the block modifier specifically includes the following steps:
s1, adding 2.3-2.5mol of 2-amino-5- (hydroxymethyl) thiazole, 20-25g of p-toluenesulfonic acid and 4-6L of acetone solvent into a reaction kettle, heating to 60-65 ℃ while stirring, dividing into 5 batches, adding 1mol of N, N' -1, 3-phenylene bismaleimide into each batch, wherein the time interval of each batch is 30min, keeping the temperature and continuing stirring for 2.5-3h after the addition is finished, pouring reaction liquid into 2L of absolute ethyl alcohol after the reaction is finished, standing for 1h, filtering, washing for 3-5 times by using the absolute ethyl alcohol, and obtaining an intermediate A after vacuum drying; the yield is 92.5%;
s2, adding the intermediate A prepared in the step S1 and 35-40% ethanol water solution of 3-4L solvent into a reaction kettle, heating to 70-80 ℃ while stirring, dropwise adding 2.1-2.3mol of dimethyl sulfate, continuing to perform heat preservation reaction for 3.5-4h after dropwise adding is finished, removing the solvent and unreacted dimethyl sulfate by reduced pressure distillation after the reaction is finished, and washing the crude product for 3-5 times by anhydrous ether to obtain a block modifier B;
the detection result is that the following substances are obtained by GC-MS: the molecular weight of the block modifier B is 586.175.
Example 2
The preparation method of the antibacterial wear-resistant synthetic leather specifically comprises the following steps:
first step, preparation of modified polyurethane resin
Adding 150g of dehydrated polypropylene glycol (PPG2000) into a reaction kettle, then adding 20g of dried block modifier B, 2g of chain extender pentaerythritol, 0.03g of catalyst dibutyltin dilaurate and 450ml of solvent DMF, heating to 60 ℃, then adding 45g of isophorone diisocyanate into the reaction kettle, heating to 80 ℃, and carrying out heat preservation reaction for 4 hours to obtain modified polyurethane resin;
and secondly, adopting a wet manufacturing process to permeate the modified polyurethane resin into the non-woven fabric, thus obtaining the antibacterial wear-resistant synthetic leather.
Example 3
The preparation method of the antibacterial wear-resistant synthetic leather specifically comprises the following steps:
first step, preparation of modified polyurethane resin
Adding 130g of dehydrated polypropylene glycol (PPG2000) into a reaction kettle, then adding 24g of dried block modifier B, 4g of chain extender pentaerythritol, 0.03g of catalyst dibutyltin dilaurate and 500ml of solvent DMF, heating to 65 ℃, then adding 50g of isophorone diisocyanate into the reaction kettle, heating to 80 ℃, and carrying out heat preservation reaction for 4 hours to obtain modified polyurethane resin;
and secondly, adopting a wet manufacturing process to permeate the modified polyurethane resin into the non-woven fabric, thus obtaining the antibacterial wear-resistant synthetic leather.
Example 4
The preparation method of the antibacterial wear-resistant synthetic leather specifically comprises the following steps:
first step, preparation of modified polyurethane resin
Adding 140g of dehydrated polypropylene glycol (PPG2000) into a reaction kettle, then adding 30g of dried block modifier B, 4g of chain extender pentaerythritol, 0.03g of catalyst dibutyltin dilaurate and 490ml of solvent DMF, heating to 60 ℃, then adding 49g of isophorone diisocyanate into the reaction kettle, heating to 85 ℃, and carrying out heat preservation reaction for 5 hours to obtain modified polyurethane resin;
and secondly, adopting a wet manufacturing process to permeate the modified polyurethane resin into the non-woven fabric, thus obtaining the antibacterial wear-resistant synthetic leather.
Comparative example 1
The remainder of the process was the same as in example 4 except that the block modifier B was not added.
Comparative example 2
The chain extender pentaerythritol was replaced with 1,4 butanediol, as in example 4.
Performance test of the synthetic leathers prepared in examples 2 to 4 and comparative examples 1 to 2
First, antibacterial property test
TABLE I, bacteriostasis rate of new-made synthetic leather
Note: the cleaning in table one is scrubbing with a pelargonium bead-leather cleaner.
Second, abrasion resistance test
The synthetic leathers prepared in examples 2 to 4 and comparative examples 1 to 2 were cut into 5 × 5cm pieces, respectively2At room temperature, a circular grinding wheel (made of sand grains) is contacted with a wafer-shaped test sample, the load is 1kg, and the rotating speed is 70rpm/min until the synthetic leather is cracked. And after the test is finished, calculating the number of turns of the wafer-shaped test sample as a coefficient for measuring the wear resistance of the synthetic leather.
TABLE II, abrasion resistance test result of synthetic leather
As can be seen from the table I and the table II, the synthetic leather prepared by modifying polyurethane with the block modifier has better antibacterial property and wear resistance.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. An antibiotic wear-resisting synthetic leather which characterized in that: the synthetic leather is prepared from modified polyurethane resin by a wet manufacturing process.
2. A preparation method of antibacterial wear-resistant synthetic leather is characterized by comprising the following steps: the method specifically comprises the following steps:
first step, preparation of Block modifier
S1, adding 2.3-2.5mol of 2-amino-5- (hydroxymethyl) thiazole, 20-25g of acid catalyst and 4-6L of solvent acetone into a reaction kettle, heating to 60-65 ℃ while stirring, dividing into 5 batches equally, adding 1mol of N, N' -1, 3-phenylene bismaleimide, keeping the temperature and continuing stirring for 2.5-3h after the addition is finished, pouring the reaction solution into 2L of absolute ethyl alcohol after the reaction is finished, standing for 1h, filtering, washing for 3-5 times by using the absolute ethyl alcohol, and drying in vacuum to obtain an intermediate A;
s2, adding the intermediate A prepared in the step S1 and 3-4L of solvent into a reaction kettle, heating to 70-80 ℃ while stirring, dropwise adding 2.1-2.3mol of dimethyl sulfate, continuing to perform heat preservation reaction for 3.5-4 hours after dropwise adding, removing the solvent and unreacted dimethyl sulfate by reduced pressure distillation after the reaction is finished, and washing a crude product for 3-5 times by anhydrous ether to obtain a block modifier B;
second step, preparation of modified polyurethane resin
Adding dehydrated polypropylene glycol into a reaction kettle, adding a dried block modifier B, a chain extender, a catalyst and a solvent DMF, heating to 60-65 ℃, adding isophorone diisocyanate into the reaction kettle, heating to 80-85 ℃, and carrying out heat preservation reaction for 4-5 hours to obtain modified polyurethane resin;
and thirdly, penetrating the modified polyurethane resin into the non-woven fabric by adopting a wet manufacturing process to obtain the antibacterial wear-resistant synthetic leather.
3. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in step S1, the acid catalyst is p-toluenesulfonic acid.
4. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in step S1, the time interval for adding N, N' -1, 3-phenylene bismaleimide to each batch is 30 min.
5. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in step S2, the solvent is 35-40% ethanol aqueous solution.
6. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in the second step, the mass ratio of the isophorone diisocyanate, the polyester polyol, the block modifier B, the chain extender and the catalyst is 45-50: 130-150:20-30:2-4:0.03.
7. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in the second step, the polyester polyol is PPG 2000.
8. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in the second step, the chain extender is pentaerythritol.
9. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in the second step, the catalyst is dibutyltin dilaurate.
10. The preparation method of the antibacterial and wear-resistant synthetic leather according to claim 2, characterized by comprising the following steps: in the second step, the liquid-mass ratio of the solvent DMF to isophorone diisocyanate was 10ml:1 g.
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