CN110818875A - Organic silicon modified polyurethane, application thereof and preparation method of coated fabric of organic silicon modified polyurethane - Google Patents
Organic silicon modified polyurethane, application thereof and preparation method of coated fabric of organic silicon modified polyurethane Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 82
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 22
- 239000010703 silicon Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920002545 silicone oil Polymers 0.000 claims abstract description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000011527 polyurethane coating Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 14
- 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 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 8
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 claims abstract 5
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 23
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- 239000002904 solvent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002310 reflectometry 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/61—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses organic silicon modified polyurethane, application thereof and a preparation method of a coated fabric thereof, wherein the preparation method comprises the following steps: (a) drying polyethylene glycol, hydroxyl silicone oil and DMBA in vacuum, heating and activating a 4A molecular sieve, and absorbing water; (b) adding polyethylene glycol, hydroxyl silicone oil, IPDI and acetone for reaction; (c) adding DMBA and dibutyl tin dilaurate, reacting, and cooling; (d) adding glycidol and acetone, reducing the temperature of the system, adding TEA, stirring and neutralizing to form salt; (e) performing rotary evaporation and purifying the modified polyurethane; (f) padding and sizing to obtain the modified polyurethane coating fabric. The organic silicon modified polyurethane is prepared by the preparation method of the organic silicon modified polyurethane coating fabric. The organosilicon modified polyurethane is used for fabric deepening. The preparation method disclosed by the invention is simple in preparation process and low in cost, not only can improve the color depth of the fabric, but also has excellent friction-resistant durability, and is beneficial to prolonging the service life of the fabric product.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to organic silicon modified polyurethane, application thereof and a preparation method of a coated fabric thereof.
Background
In recent years, the problem of the depth of color of dyed fabrics has been receiving attention due to the influence of factors such as balanced dye uptake and fastness of dyeing of fibers. When the fabric is dyed, the color depth of the fabric is insufficient due to the reasons of low dye-uptake rate or low fixation rate, and the like, so that the current situation is changed by needing a deepening agent to meet higher and tighter requirements of the market on coated fabrics, reduce the production cost and reduce the use amount of dyes and coatings.
Nowadays, silicone deepening agents are commonly used, and the silicone resin has the advantages of low refractive index, low surface energy, good reactivity, adsorbability, flexibility, no pollution and the like. However, when the organic silicon resin is used as a coating fabric deepening agent, the adhesion with a coating is poor, and the problems of the dyeing depth and the fastness of the coating fabric cannot be effectively solved.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide a preparation method of an organosilicon modified polyurethane coated fabric which has deepening property and can be cured on the surface of the fabric to improve the fastness to washing of the fabric.
The technical scheme is as follows: the preparation method of the organic silicon modified polyurethane coating fabric comprises the following steps:
a. putting polyethylene glycol, hydroxyl silicone oil and 2, 2-dimethylolbutyric acid (DMBA) into a vacuum drying oven at the temperature of 80-90 ℃ for heating for 12-14 h, removing water in reaction raw materials, heating and activating a 4A molecular sieve at the temperature of 600-650 ℃ by using a vacuum tube type high-temperature sintering furnace for 4-5 h, putting the molecular sieve into acetone for absorbing water, and using the molecular sieve after treating for 7-8 d;
b. setting up a reaction device by using an oil bath heating and mechanical stirring manner, adding polyethylene glycol with the molecular weight of 400-1000 and hydroxy silicone oil with the molecular weight of 400-1000 into a three-neck flask with a condensation pipe, wherein the dropping speed of the polyethylene glycol and the hydroxy silicone oil is 1-2 drops/s, n (polyethylene glycol) and n (hydroxy silicone oil) are 1-3: 2, the stirring speed is 200-300 r/min, adding IPDI and acetone, reacting at 70-75 ℃ for 2-3 h, and n (IPDI) and n (polyethylene glycol and hydroxy silicone oil) are 20: 9-10;
c. adding chain extender DMBA, wherein n (IPDI) and n (DMBA) are 4: 1-2, simultaneously adding 2-3 drops of dibutyl tin dilaurate catalyst, stirring at 350-400 r/min, reacting for 2-3 h at 70-75 ℃, cooling by using an ice bag, and slowly cooling to 60-65 ℃ at a cooling speed of 0.5 ℃/min;
d. adding 70-80 ml of glycidol and 12-15 mol of solvent acetone in total volume in a blocking stage, reacting for 1-1.5 h at 60-65 ℃ and a stirring speed of 200-300 r/min, cooling the system temperature to 40-45 ℃, adding Triethylamine (TEA) with the neutralization degree of 100%, wherein n (IPDI) to n (glycidol) to n (TEA) is 10: 1-2: 1, and stirring for 30-50 min to form a salt, thereby obtaining the glycidol-blocked organosilicon modified waterborne polyurethane;
e. carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, and purifying the modified polyurethane;
f. the modified polyurethane coating fabric is obtained by padding for 3-4 min, padding liquor ratio of 70-80%, pre-drying at 70-80 ℃, then baking at 120-125 ℃ for 2-3 min, and shaping.
Wherein, the glycidol is prepared by heating monochloropropanediol and 1, 2-dichloroethane for 1-1.5 h until boiling, then adding sodium hydroxide in batches, filtering and distilling.
The organic silicon modified polyurethane prepared by the preparation method of the organic silicon modified polyurethane coating fabric has high film forming property and good adhesion. When the hydroxyl silicone oil modified polyurethane is prepared, the performance of the synthesized organic silicon modified polyurethane is controlled by controlling the molecular weight of the hydroxyl silicone oil and the polyethylene glycol and the ratio of the hardness to the softness. The film forming property is ensured, and the deepening effect is maximized. And the main chain of the hydroxyl silicone oil consists of a-Si-O-Si-skeleton, methyl is connected with silicon atoms to form a side group, and the silicon-oxygen bond in the main chain has large volume and low internal energy density, so that the special structure and composition can effectively improve the performances of the polyurethane such as weather resistance, thermal stability, wear resistance and the like.
The application of the organosilicon modified polyurethane in fabric deepening can be combined with fabric while increasing the color depth of the fabric, and the washing fastness of the fabric is improved.
The processing principle is as follows: the hydroxyl silicone oil is added in the prepolymerization stage to synthesize the modified prepolymer, the organic silicon is connected into the polyurethane chain segment, the refractive index of the polyurethane is effectively reduced, when the modified polyurethane is subjected to thermosetting on the surface of the fabric and the epoxy group ring opening contained in the polyurethane reacts with the hydroxyl group on the fabric to be tightly combined to form a coating, due to the existence of the organic silicon, light irradiates on the surface of the fabric, reflected light is reduced, the incident light quantity is increased, and the color depth of the surface of the fabric is increased. The modified polyurethane forms a coating on the surface of the fabric, so that the dye on the surface of the fabric can be effectively covered, the washing fastness, the rubbing fastness and the like of the fabric are improved, and the tensile property of the fabric is further improved due to the existence of the coating.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the organic silicon chain segment is connected into the polyurethane prepolymer in the prepolymerization stage, the refractive index of polyurethane can be effectively reduced due to the existence of the organic silicon in the polyurethane chain segment, and after high-temperature shaping and finishing, the hydroxyl silicone oil modified polyurethane is cured on the surface of the fabric to form a film, so that the color depth of the fabric is increased;
2. the preparation method disclosed by the invention is simple in preparation process, low in cost of used reagents, and suitable for most processes, can improve the color depth of the fabric, has excellent friction-resistant durability, does not generate damage phenomena such as falling even if subjected to large friction, and is beneficial to prolonging the service life of the fabric product.
Drawings
FIG. 1 is the deepening principle of the organosilicon modified polyurethane of the invention;
FIG. 2 is an infrared spectrum of the modified polyurethane obtained in example 4 of the present invention;
FIG. 3 is a graph showing the particle size distribution of the emulsion for the modified polyurethane-finished fabric obtained in example 4 of the present invention.
Detailed Description
The reaction mechanism of the silane coupling agent having an epoxy group with the fabric is as follows:
the darkening principle of the organosilicon modified polyurethane is shown in fig. 1, and the reflection rate of the surface of the fabric is reduced, so that the reflected light of the surface of the fabric is reduced, the transmitted light is increased, and the color depth of the fabric is increased.
Example 1
(1) Polyethylene glycol 400 (molecular weight), hydroxyl silicone oil 400 (molecular weight) and 2, 2-dimethylolbutyric acid (DMBA) are put into a vacuum drying oven and heated for 12 hours at 87 ℃, and the moisture in the reaction raw materials is removed. Heating the 4A molecular sieve for 4h at 600 ℃ by using a vacuum tube type high-temperature sintering furnace, activating, putting into acetone to adsorb water, and using after one week of treatment;
(2) setting up a reaction device by using an oil bath heating and mechanical stirring mode, adding 0.3mol of polyethylene glycol and 0.6mol of hydroxyl silicone oil into a three-neck flask with a condenser pipe, adding 2mol of IPDI and 10mol of acetone, reacting for 2 hours at 70 ℃ and at a stirring speed of 200r/min, and dropwise adding 2 drops/s of polyethylene glycol 400 and hydroxyl silicone oil 400 by using a constant-pressure funnel;
(3) then adding 1mol of DMBA as a chain extender, simultaneously adding 2 drops of dibutyl tin dilaurate as a catalyst, reacting at 70 ℃ and a stirring speed of 350r/min for 2h, and slowly cooling to 60 ℃;
(4) and in the end capping stage, 0.2mol of glycidol is added, 12mol of acetone solvent is added simultaneously, the stirring speed of a stirring rod is 280r/min, and the reaction is carried out for 1.5h at the temperature of 60 ℃. Then cooling the system temperature to 40 ℃, adding 1mol of Triethylamine (TEA) according to 100% of neutralization degree, stirring for 50min to form salt, and obtaining the organic silicon modified waterborne polyurethane terminated by the glycidyl silicone oil;
(5) carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, removing unreacted substances and solvent acetone in the system, and purifying the modified polyurethane;
(6) the fabric is soaked in 30g/L modified polyurethane emulsion for finishing for 3min, then is rolled, the rolling liquor rate is 70%, the fabric is pre-dried at 70 ℃, and then is shaped at high temperature of 120 ℃ for 3min to process a fabric sample, so that the modified polyurethane coating fabric is obtained.
Example 2
(1) Polyethylene glycol 1000, hydroxyl silicone oil 1000 and 2, 2-dimethylolbutyric acid (DMBA) are put into a vacuum drying oven and heated for 14 hours at 82 ℃, and the moisture in the reaction raw materials is removed. Heating the 4A molecular sieve for 5 hours at 650 ℃ by using a vacuum tube type high-temperature sintering furnace, activating, putting into acetone to adsorb moisture, and treating for 8 days;
(2) the method comprises the following steps of (1) building a reaction device by using an oil bath heating and mechanical stirring mode, adding 0.45mol of polyethylene glycol 0.45mol of hydroxyl silicone oil into a three-neck flask with a condenser pipe, adding 2mol of IPDI and 10mol of acetone, reacting for 3 hours at 75 ℃ and at the stirring speed of 300r/min, and dropwise adding 2 drops/s of polyethylene glycol 1000 and hydroxyl silicone oil 1000 by using a constant-pressure funnel;
(3) then adding 0.5mol of DMBA as a chain extender, simultaneously adding 3 drops of dibutyl tin dilaurate as a catalyst, reacting at 75 ℃ and a stirring speed of 400r/min for 3h, and slowly cooling to 65 ℃;
(4) and in the end capping stage, 0.2mol of glycidol is added, 15mol of acetone solvent is added at the same time, the stirring speed of a stirring rod is 220r/min, and the reaction is carried out for 1h at 65 ℃. Then cooling the system temperature to 45 ℃, adding 1mol of Triethylamine (TEA) with the neutralization degree of 100%, stirring for 30min to form salt, and obtaining the silicone modified waterborne polyurethane terminated by the glycidyl silicone oil;
(5) carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, removing unreacted substances and solvent acetone in the system, and purifying the modified polyurethane;
(6) the fabric is soaked in 30g/L modified polyurethane emulsion for finishing for 4min, then is rolled, the rolling liquor rate is 80%, the fabric is pre-dried at 80 ℃, and then is shaped at high temperature of 120 ℃ for 2min to process a fabric sample, so that the modified polyurethane coating fabric is obtained.
Example 3
(1) Polyethylene glycol 400, hydroxyl silicone oil 400 and 2, 2-dimethylolbutyric acid (DMBA) are put into a vacuum drying oven and heated for 13 hours at the temperature of 85 ℃, and the moisture in the reaction raw materials is removed. Heating the 4A molecular sieve for 4.5h at 625 ℃ by using a vacuum tube type high-temperature sintering furnace, activating, putting into acetone to adsorb water, and using after one week of treatment;
(2) the method comprises the following steps of (1) building a reaction device by using an oil bath heating and mechanical stirring mode, adding 0.6mol of polyethylene glycol and 0.4mol of hydroxyl silicone oil into a three-neck flask with a condensing tube, adding 2mol of IPDI and 10mol of acetone, reacting for 2.5h at the stirring speed of 250r/min at 72 ℃, and dropwise adding 2 drops/s of polyethylene glycol 400 and hydroxyl silicone oil 400 by using a constant-pressure funnel;
(3) then adding 1mol of DMBA as a chain extender, simultaneously adding 2 drops of dibutyl tin dilaurate as a catalyst, reacting at 73 ℃ and a stirring speed of 375r/min for 2.5h, and slowly cooling to 63 ℃;
(4) and in the end-capping stage, 0.2mol of glycidol is added, 13mol of acetone solvent is added at the same time, the stirring speed of a stirring rod is 200r/min, and the reaction is carried out for 1h at 63 ℃. Then cooling the system temperature to 43 ℃, adding 1mol of Triethylamine (TEA) according to 100% of neutralization degree, stirring for 40min to form salt, and obtaining the organic silicon modified waterborne polyurethane terminated by the glycidyl silicone oil;
(5) carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, removing unreacted substances and solvent acetone in the system, and purifying the modified polyurethane;
(6) the fabric is soaked in 30g/L modified polyurethane emulsion for finishing for 3min, then is rolled, the mangling liquor rate is 75%, and is pre-dried at the temperature of 75 ℃, and then is shaped at the high temperature of 120 ℃ for 2.5min to process a cloth sample, so that the modified polyurethane coating fabric is obtained.
Example 4
(1) Polyethylene glycol 600, hydroxyl silicone oil 600 and 2, 2-dimethylolbutyric acid (DMBA) are put into a vacuum drying oven and heated for 12 hours at the temperature of 80 ℃, and the moisture in the reaction raw materials is removed. Heating the 4A molecular sieve for 4h at 610 ℃ by using a vacuum tube type high-temperature sintering furnace, activating, putting into acetone to adsorb water, and using after treating for one week;
(2) the method comprises the following steps of (1) building a reaction device by using an oil bath heating and mechanical stirring mode, adding 0.3mol of polyethylene glycol and 0.6mol of hydroxyl silicone oil into a three-neck flask with a condensation pipe, adding 2mol of IPDI and 10mol of acetone, reacting for 2 hours at 71 ℃ and at a stirring speed of 220r/min, and dropwise adding 2 drops/s of polyethylene glycol 600 and hydroxyl silicone oil 600 by using a constant-pressure funnel;
(3) then adding 1mol of DMBA as a chain extender, simultaneously adding 2 drops of dibutyl tin dilaurate as a catalyst, reacting at 72 ℃ and a stirring speed of 360r/min for 2h, and then slowly cooling to 62 ℃;
(4) in the end-capping stage, 0.4mol of glycidol is added, 14mol of acetone solvent is added at the same time, the stirring speed of a stirring rod is 300r/min, and the reaction is carried out for 1.5h at 61 ℃. Then cooling the system temperature to 41 ℃, adding 1mol of Triethylamine (TEA) according to 100% of neutralization degree, stirring for 35min to form salt, and obtaining the organic silicon modified waterborne polyurethane terminated by the glycidyl silicone oil;
(5) carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, removing unreacted substances and solvent acetone in the system, and purifying the modified polyurethane;
(6) the fabric is soaked in 30g/L modified polyurethane emulsion for finishing for 3min, then is rolled, the mangling liquor rate is 72 percent, and is pre-dried at 73 ℃, and then is shaped at high temperature of 120 ℃ for 2min to process a cloth sample, so that the modified polyurethane coating fabric is obtained.
Example 5
(1) Polyethylene glycol 800, hydroxyl silicone oil 400 and 2, 2-dimethylolbutyric acid (DMBA) are put into a vacuum drying oven and heated for 14 hours at the temperature of 90 ℃, and the moisture in the reaction raw materials is removed. Heating the 4A molecular sieve for 5 hours at 640 ℃ by using a vacuum tube type high-temperature sintering furnace, activating, putting into acetone to adsorb water, and using after treating for one week;
(2) setting up a reaction device by using an oil bath heating and mechanical stirring mode, adding 0.3mol of polyethylene glycol and 0.6mol of hydroxyl silicone oil into a three-neck flask with a condenser pipe, adding 2mol of IPDI and 12mol of acetone, reacting for 2 hours at 74 ℃ and a stirring speed of 280r/min, and dropwise adding 2 drops/s of polyethylene glycol 800 and hydroxyl silicone oil 400 by using a constant-pressure funnel;
(3) then adding 1mol of DMBA as a chain extender, simultaneously adding 2 drops of dibutyl tin dilaurate as a catalyst, reacting at 74 ℃ and a stirring speed of 390r/min for 3 hours, and slowly cooling to 64 ℃;
(4) and in the end capping stage, 0.2mol of glycidol is added, 2mol of acetone solvent is added at the same time, the stirring speed of a stirring rod is 250r/min, and the reaction is carried out for 1.5h at 64 ℃. Then cooling the system temperature to 44 ℃, adding 1mol of Triethylamine (TEA) according to 100% of neutralization degree, stirring for 45min to form salt, and obtaining the organic silicon modified waterborne polyurethane terminated by the glycidyl silicone oil;
(5) carrying out rotary evaporation on the synthesized hydroxyl silicone oil modified polyurethane solution, removing unreacted substances and solvent acetone in the system, and purifying the modified polyurethane;
(6) the fabric is soaked in 30g/L modified polyurethane emulsion for finishing for 3min, then is rolled, the mangling liquor rate is 78%, the fabric is pre-dried at 78 ℃, and then is shaped at high temperature of 120 ℃ for 3min to process a fabric sample, so that the modified polyurethane coating fabric is obtained.
TABLE 1 darkening effect of fabrics finished with different concentrations of finishing liquor in example 4
| Sample (I) | L* | a* | b* | C* | h* | K/S | Depth increase rate |
| Raw fabric | 33.11 | -1.57 | -36.42 | 36.45 | 267.53 | 16.649 | - |
| 10g/L finishing | 31.97 | -1.72 | -37.12 | 37.13 | 268.89 | 18.476 | 10.97％ |
| 20g/L finishing | 29.79 | -1.47 | -36.22 | 37.02 | 268.17 | 21.611 | 29.80％ |
| 30g/L finishing | 29.91 | -1.28 | -36.31 | 36.88 | 268.3 | 21.428 | 28.70％ |
| 60g/L finishing | 31.4 | -1.07 | -36.4 | 36.42 | 268.32 | 19.19 | 15.26％ |
Where L represents lightness, a represents a range from magenta to green, b represents a range from yellow to blue, and K/S represents a color depth of the fabric.
Examples 1 to 5 are silicone modified polyurethanes prepared under the conditions of polyethylene glycol of different molecular weights and polyethylene glycol of different soft segment ratios and hydroxy silicone oil, wherein the silicone modified polyurethane prepared in example 1 has the best performance and the best curing performance, can be completely solidified within 5 to 7 seconds after thermosetting in an oven, and has a deepening effect 0.7 to 1.2 percent higher than that of the other polyurethane under the same dosage. The infrared spectrum was used to determine whether the synthesis of the modified polyurethane prepared in example 4 was successful, as shown in FIG. 2, from 790cm-1The hydroxy silicone oil has a stretching vibration absorption peak of Si-O-Si, which shows that the hydroxy silicone oil is successfully grafted in. The prepared organic silicon modified polyurethane darkening finishing agent can be rapidly formed into a film on the surface layer of the fabric after high-temperature shaping, and the tensile fastness of the fabric can be effectively improved due to the existence of a polyurethane film. The cured film is colorless and does notThe color of the fabric is affected, the K/S value of the fabric finished in the hydroxy silicone oil modified polyurethane solution with the K/S value of 20-30 g/L before and after finishing, which is prepared in the test example 4, is the largest, the particle size distribution of the solution is uniform, the solution temperature is high, and a cured film formed on the surface of the finished fabric effectively reduces the reflectivity of incident light on the surface of the fabric, increases the incident light, and the depth increasing rate of the fabric reaches 10-28%.
Claims (10)
1. A preparation method of an organic silicon modified polyurethane coating fabric is characterized by comprising the following steps:
(a) drying polyethylene glycol, hydroxyl silicone oil and DMBA in vacuum, heating and activating a 4A molecular sieve at 600-650 ℃, putting the molecular sieve into acetone to adsorb water, and using the molecular sieve after treating for 7-8 days;
(b) adding polyethylene glycol and hydroxyl silicone oil into a three-neck flask with a condenser pipe, performing oil bath and mechanical stirring, adding IPDI and acetone, and reacting for 2-3 h at 70-75 ℃;
(c) adding chain extender DMBA, adding 2-3 drops of dibutyl tin dilaurate catalyst, stirring at 70-75 ℃ for reaction for 2-3 h, slowly cooling to 60-65 ℃, wherein the cooling speed is 0.5 ℃/min;
(d) adding glycidol and acetone, stirring and reacting for 1-1.5 h at 60-65 ℃, cooling the system temperature to 40-45 ℃, adding TEA with the neutralization degree of 100%, stirring for 30-50 min to form salt, and obtaining the glycidol-terminated organosilicon modified waterborne polyurethane;
(e) d, performing rotary evaporation on the solution obtained in the step d, and purifying the modified polyurethane;
(f) and (3) carrying out padding and shaping treatment on the cloth sample to obtain the modified polyurethane coating fabric.
2. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: the temperature of vacuum drying in the step (a) is 80-90 ℃, the time is 12-14 h, and the activation treatment time is 4-5 h.
3. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: in the step (b), the molecular weight of the polyethylene glycol is 400-1000, the molecular weight of the hydroxyl silicone oil is 400-1000, n (polyethylene glycol) and n (hydroxyl silicone oil) are 1-3: 2, and the dropping speed of the polyethylene glycol and the hydroxyl silicone oil is 1-2 drops/s.
4. The preparation method of the organosilicon modified polyurethane coating fabric according to claim 3, wherein the preparation method comprises the following steps: in the step (b), n (IPDI) and n (polyethylene glycol + hydroxyl silicone oil) are 20: 9-10.
5. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: in the step (b), the stirring speed of mechanical stirring is 200-300 r/min.
6. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: in the step (c), the stirring speed is 350-400 r/min, and n (IPDI) and n (DMBA) are 4: 1-2.
7. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: in the step (d), n (IPDI), n (glycidol), n (TEA) and the like are 10: 1-2: 5, the stirring speed of a stirring rod is 200-300 r/min, and the total amount of acetone added in the experimental process is 12-15 mol.
8. The method for preparing the organosilicon modified polyurethane coating fabric according to claim 1, wherein the method comprises the following steps: in the step (f), padding time is 3-4 min, mangle rolling rate is 70-80%, pre-drying is carried out at 70-80 ℃, and then baking is carried out at 120-125 ℃ for 2-3 min.
9. The silicone-modified polyurethane prepared by the method for preparing a silicone-modified polyurethane coated fabric according to any one of claims 1 to 8.
10. Use of the silicone-modified polyurethane of claim 9 for fabric darkening.
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