CN116554432A - Black paste for solvent-free polyurethane synthetic leather and preparation method thereof - Google Patents
Black paste for solvent-free polyurethane synthetic leather and preparation method thereof Download PDFInfo
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- CN116554432A CN116554432A CN202310532371.3A CN202310532371A CN116554432A CN 116554432 A CN116554432 A CN 116554432A CN 202310532371 A CN202310532371 A CN 202310532371A CN 116554432 A CN116554432 A CN 116554432A
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- solvent
- synthetic leather
- free polyurethane
- polyurethane synthetic
- black paste
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 38
- 229920000570 polyether Polymers 0.000 claims abstract description 38
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000006229 carbon black Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 238000000227 grinding 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
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000004040 coloring Methods 0.000 abstract description 10
- 239000010985 leather Substances 0.000 abstract description 6
- 239000000049 pigment Substances 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 13
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a black paste for solvent-free polyurethane synthetic leather and a preparation method thereof, and relates to the field of pigment chemical industry. The preparation method comprises the following steps: 1) Mixing polyether polyol and carbon black, and then performing pre-drying dehydration to obtain a pre-drying dehydrated material; 2) Adding isophorone diisocyanate and a catalyst into the pre-baked dehydrated material obtained in the step 1) to react to obtain a mixed material; 3) And (3) cooling the mixed material obtained in the step (2), adding a dispersing agent for dispersing, and grinding to obtain the black paste for the solvent-free polyurethane synthetic leather. The invention solves the problems that the existing black paste can not meet the coloring requirement and influence the reaction of solvent-free synthetic leather, and the prepared color paste has high pigment content, meets the coloring requirement, has low viscosity, can realize pipeline transportation and on-line batching, has the advantages of low hydroxyl value of the color paste and low moisture content, and can reduce the consumption of isocyanate in the synthetic leather reaction process, thereby enhancing the peeling strength and wear resistance of the finished leather.
Description
Technical Field
The invention relates to the field of pigment chemical industry, in particular to a black paste for solvent-free polyurethane synthetic leather and a preparation method thereof.
Background
The solvent-free polyurethane synthetic leather is one of the important solutions for environmental protection synthetic leather as a new generation synthetic leather technology. Unlike conventional DMF solvent-type synthetic leather, solvent-free polyurethane synthetic leather has the following advantages: 1. DMF organic solvent is not needed in the manufacturing process, VOC emission is reduced, and zero DMF addition of the finished leather can be realized; 2. has higher peel strength and wear resistance. Therefore, the solvent-free polyurethane synthetic leather is increasingly applied to the fields of high-grade furniture, shoes, bags, automotive interiors, electronic packages and the like.
Generally, the solvent-free polyurethane synthetic leather is applied to the bottom material, and the coloring requirement is rarely met, but with the improvement of the quality requirement of the solvent-free synthetic leather in the market and the application of more and more solvent-free polyurethane synthetic leather to the surface layer, the requirement of the solvent-free polyurethane synthetic leather on the coloring is also higher and higher. The solvent-free polyurethane synthetic leather is an online synthetic reaction process of polyol and isocyanate, and the following requirements are met for the addition of color paste: 1. the solid is high, the viscosity is low, the carbon black content is high, the color paste addition amount is reduced, the viscosity is low, and the pipeline transportation and the on-line batching can be realized; 2. the hydroxyl value of the color paste is low; 3. the moisture content in the color paste is low. When the hydroxyl value of the color paste is high or the water content in the color paste is high, part of isocyanate can be reacted, so that the reaction process of the synthetic leather is influenced, and the peeling strength and the abrasion resistance of the finished leather are reduced.
The black paste for the solvent-free polyurethane synthetic leather commonly used in the market at present mostly uses polyether polyol as a carrier and is ground by adding carbon black. The polyether polyol with high molecular weight and low hydroxyl value has higher viscosity and is not suitable for being used as a color paste carrier; when a low-viscosity low-molecular-weight polyether polyol is used as a carrier, the high hydroxyl value of the polyether polyol causes a new problem: the addition amount of the color paste is low and can not meet the coloring requirement; the high addition amount of the color paste affects the reaction of the solvent-free polyurethane synthetic leather, and the finished product is bad.
Therefore, how to provide a color paste which can meet the coloring requirement of solvent-free synthetic leather and does not influence the reaction of the solvent-free synthetic leather is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to provide a black paste for solvent-free polyurethane synthetic leather and a preparation method thereof, and solves the problems that the existing black paste cannot meet the coloring requirement of solvent-free synthetic leather and influence the reaction of the solvent-free synthetic leather.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of black paste for solvent-free polyurethane synthetic leather, which comprises the following steps:
1) Mixing polyether polyol and carbon black, and then performing pre-drying dehydration to obtain a pre-drying dehydrated material;
2) Adding isophorone diisocyanate and a catalyst into the pre-baked dehydrated material obtained in the step 1) to react to obtain a mixed material;
3) And (3) cooling the mixed material obtained in the step (2), adding a dispersing agent for dispersing, and grinding to obtain the black paste for the solvent-free polyurethane synthetic leather.
Preferably, the raw materials comprise the following components in parts by weight: 90-110 parts of polyether polyol, 22-32 parts of carbon black, 5-6 parts of isophorone diisocyanate, 0.02-0.03 part of catalyst and 3-6 parts of dispersing agent.
Preferably, the polyether polyol comprises a double-ended hydroxyl polyether polyol or a triple-ended hydroxyl polyether polyol.
Preferably, the dispersant comprises an organic amine modified polyurethane, an organic amine modified polyamide or an organic amine modified polyether.
Preferably, the catalyst comprises organobismuth.
Preferably, the temperature of the pre-baking dehydration in the step 1) is 110-120 ℃ and the time is 30-40 min;
the pre-baking dehydration is carried out under the stirring condition, and the stirring speed is 80-100 r/min.
Preferably, the temperature of the reaction in the step 2) is 80-90 ℃ and the time is 120-150 min;
the reaction is carried out under the condition of stirring, and the stirring speed is 100-200 r/min.
Preferably, the temperature range of the temperature reduction in the step 3) is 40-45 ℃;
the dispersion is carried out under the condition of stirring, the stirring speed is 800-1000 r/min, and the stirring time is 25-30 min;
the grinding times are 2-4 times, and the grinding standard is that the particle size D97 is less than 5 mu m.
The invention further aims to provide the black paste for the solvent-free polyurethane synthetic leather prepared by the preparation method.
The invention firstly mixes polyether polyol and carbon black, firstly pre-dries and dehydrates in a reaction kettle, and realizes closed operation in wetting and grinding stages, thereby reducing the moisture content of color paste.
The invention can obtain the pre-polymerized polyol with low hydroxyl value (8-11 mgKOH/g) and low viscosity (400-600 cps/25 ℃) by pre-polymerizing the polyether polyol and the isophorone diisocyanate, and takes the pre-polymerized polyol as a carrier of color paste, and the prepared black paste for the solvent-free polyurethane synthetic leather has the characteristics of high carbon black content, high blackness, excellent storage stability and low viscosity, and meets the requirements of color paste.
The reason why the organic amine modified polyurethane, the organic amine modified polyamide or the organic amine modified polyether is used as the dispersing agent in the invention is that: the organic amine structure has better wettability and dispersibility for the acid carbon black, and the large molecular weight polyurethane structure has better steric effect, so that the dispersed carbon black particles are not easy to aggregate, and the stability of the color paste is further improved. The color paste is applied to coloring of a polyurethane resin system, has good application matching property, and can lead the final synthetic leather product to have good blackness and physical properties.
Different from the traditional color paste for solvent-free synthetic leather, the extra black color paste provided by the invention has the following advantages:
1. high-solid low-viscosity: the pigment content is high, the coloring requirement is met, the viscosity is low, the pipeline transportation and the on-line batching can be realized.
2. The color paste has low hydroxyl value and low moisture content: isocyanate consumption in the synthetic leather reaction process can be reduced, so that the peeling strength and the abrasion fastness of the finished leather are enhanced.
Detailed Description
The invention provides a preparation method of black paste for solvent-free polyurethane synthetic leather, which comprises the following steps:
1) Mixing polyether polyol and carbon black, and then performing pre-drying dehydration to obtain a pre-drying dehydrated material;
2) Adding isophorone diisocyanate and a catalyst into the pre-baked dehydrated material obtained in the step 1) to react to obtain a mixed material;
3) And (3) cooling the mixed material obtained in the step (2), adding a dispersing agent for dispersing, and grinding to obtain the black paste for the solvent-free polyurethane synthetic leather.
In the invention, the raw materials are as follows in parts by weight: the amount of polyether polyol added is preferably 90 to 110 parts, more preferably 95 to 105 parts, still more preferably 98 to 102 parts; the amount of carbon black to be added is preferably 22 to 32 parts, more preferably 25 to 30 parts, still more preferably 26 to 28 parts; the amount of isophorone diisocyanate to be added is preferably 5 to 6 parts, more preferably 5.2 to 5.8 parts, still more preferably 5.4 to 5.6 parts; the amount of the catalyst to be added is preferably 0.02 to 0.03 part, more preferably 0.022 to 0.028 part, still more preferably 0.024 to 0.026 part; the amount of the dispersant to be added is preferably 3 to 6 parts, more preferably 4 to 5 parts.
In the present invention, the temperature of the pre-baking dehydration in the step 1) is preferably 110 to 120 ℃, more preferably 112 to 118 ℃, and even more preferably 114 to 116 ℃; the time is preferably 30 to 40 minutes, more preferably 32 to 38 minutes, and still more preferably 34 to 36 minutes;
the preliminary drying and dehydration are preferably performed under stirring, and the stirring rate is preferably 80 to 100r/min, more preferably 85 to 95r/min, and even more preferably 90r/min.
In the present invention, the polyether polyol comprises a double-ended hydroxyl polyether polyol or a triple-ended hydroxyl polyether polyol.
In the present invention, the dispersant comprises an organic amine-modified polyurethane, an organic amine-modified polyamide, or an organic amine-modified polyether.
In the present invention, the carbon black is preferably a high pigment carbon black having a high blackness.
In the present invention, the temperature of the reaction in step 2) is preferably 80 to 90 ℃, more preferably 82 to 88 ℃, still more preferably 84 to 86 ℃; the time is preferably 120 to 150 minutes, more preferably 125 to 145 minutes, and still more preferably 130 to 140 minutes;
the reaction is preferably carried out under stirring at a rate of preferably 100 to 200r/min, more preferably 120 to 180r/min, still more preferably 140 to 160r/min.
In the present invention, the catalyst comprises organobismuth.
In the present invention, the temperature range of the cooling in step 3) is preferably 40 to 45 ℃, more preferably 41 to 44 ℃, still more preferably 42 to 43 ℃;
the dispersion is preferably carried out under stirring, and the stirring rate is preferably 800 to 1000r/min, more preferably 850 to 950r/min, and even more preferably 880 to 920r/min; the stirring time is preferably 25 to 30 minutes, more preferably 26 to 29 minutes, and still more preferably 27 to 30 minutes;
the number of grinding is preferably 2 to 4, more preferably 3; the grinding standard is preferably a particle size D97<5 μm, more preferably a particle size D97<4 μm, and even more preferably a particle size D97<3 μm.
The invention further aims to provide the black paste for the solvent-free polyurethane synthetic leather prepared by the preparation method.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The double-end hydroxyl polyether polyol used in the embodiment or the comparative example of the invention is DP-3000 (hydroxyl value 33-37 mgKOH/g) of Kunshan chemical Co., ltd;
the three-terminal hydroxyl polyether polyol used in the embodiment or the comparative example is GY-3000 of Kunshan Co., ltd;
the carbon blacks used in the examples or comparative examples of the present invention are PowCarbon 53, new Anhui black cat Material Co., ltd;
the isophorone diisocyanate used in the examples or comparative examples of the present invention is cosurful IPDI;
the organobismuth used in the examples or comparative examples of the present invention was valikattbi 2010 of the grace family;
the organic amine modified polyurethane used in the examples or comparative examples of the present invention is SY-1510 of a tri-polymer;
the organic amine modified polyamide used in the examples or comparative examples of the present invention is SY-1663 of a tri-higher molecule;
the organic amine-modified polyether used in the examples or comparative examples of the present invention was SY-1236, which is a tri-polymer.
Example 1
1) 100 parts of double-end hydroxyl polyether polyol and 30 parts of carbon black are put into a reaction kettle, and pre-baked and dehydrated for 30 minutes under the conditions that the temperature of the reaction kettle is 120 ℃ and the stirring speed is 100r/min, so as to obtain a pre-baked and dehydrated material.
2) Adding 5.5 parts of isophorone diisocyanate and 0.02 part of organic bismuth into the pre-baked dehydrated material obtained in the step 1) to react, wherein the reaction temperature is 90 ℃ and the reaction time is 120min; the reaction was carried out under stirring at a stirring rate of 200r/min to obtain a mixed material.
3) And (2) cooling the mixed material obtained in the step (2) to 45 ℃, adding 5 parts of organic amine modified polyurethane for dispersion, and stirring under the stirring condition, wherein the stirring speed is 1000r/min, and the stirring time is 25min. And grinding for 2 times to obtain the black paste for the solvent-free polyurethane synthetic leather with the particle size D97 of less than 5 mu m.
Example 2
Example 2 differs from example 1 only in that the amount of carbon black added was 25 parts, and the other raw material addition amounts and process parameters were identical to those of example 1.
Example 3
1) 110 parts of three-terminal hydroxyl polyether polyol and 32 parts of carbon black are put into a reaction kettle, and pre-baked and dehydrated for 40 minutes under the conditions of the temperature of the reaction kettle of 110 ℃ and the stirring speed of 80r/min, so as to obtain a pre-baked and dehydrated material.
2) Adding 6 parts of isophorone diisocyanate and 0.03 part of organic bismuth into the pre-baked dehydrated material obtained in the step 1) to react, wherein the reaction temperature is 80 ℃ and the reaction time is 150min; the reaction was carried out under stirring at a stirring rate of 100r/min to obtain a mixed material.
3) Cooling the mixed material obtained in the step 2) to 40 ℃, adding 6 parts of organic amine modified polyamide for dispersion, and stirring under the stirring condition, wherein the stirring speed is 800r/min, and the stirring time is 25min. And grinding for 4 times to obtain the black paste for the solvent-free polyurethane synthetic leather with the particle size D97 of less than 3 mu m.
Example 4
1) 90 parts of three-terminal hydroxyl polyether polyol and 22 parts of carbon black are put into a reaction kettle, and pre-baked and dehydrated for 35 minutes under the conditions of the temperature of the reaction kettle of 110 ℃ and the stirring speed of 80r/min, so as to obtain a pre-baked and dehydrated material.
2) Adding 5 parts of isophorone diisocyanate and 0.025 part of organic bismuth into the pre-baked dehydrated material obtained in the step 1) to react at 90 ℃ for 130min; the reaction is carried out under the condition of stirring, and the stirring speed is 150r/min, so as to obtain a mixed material.
3) Cooling the mixture obtained in the step 2) to 43 ℃, adding 3 parts of organic amine modified polyether for dispersion, and stirring under the stirring condition, wherein the stirring speed is 900r/min, and the stirring time is 28min. And grinding for 3 times to obtain the black paste for the solvent-free polyurethane synthetic leather with the particle size D97 of less than 4 mu m.
Comparative example 1
1) Sequentially adding 100 parts of double-end hydroxyl polyether polyol, 30 parts of carbon black and 5 parts of dispersing agent into a reaction kettle, and dispersing for 25min at 1000 r/min;
2) Grinding the material obtained in the step 1) for 2 times to obtain the color paste for the solvent-free polyurethane synthetic leather.
Unlike example 1, comparative example 1 uses a polyether polyol as a carrier to grind color paste without prepolymerization, and carbon black is not pre-baked to dehydrate, the preparation method used in comparative example 1 is common in the market.
Comparative example 2
1) And (3) pre-drying and dehydrating 100 parts of double-end hydroxyl polyether polyol for 30min under the conditions of the temperature of a reaction kettle of 120 ℃ and the stirring speed of 100r/min to obtain pre-dried and dehydrated polyether polyol.
2) 5.5 parts of isophorone diisocyanate and 0.02 part of organic bismuth are added into the obtained pre-baked dehydrated polyether polyol to react at 90 ℃ for 120min; the reaction is carried out under the condition of stirring, and the stirring speed is 200r/min, so as to obtain the pre-polymerized polyester polyol.
3) Adding 30 parts of carbon black and 5 parts of organic amine modified polyurethane into the pre-polymerized polyester polyol obtained in the step 2) for dispersion, wherein the dispersion is carried out under the stirring condition, the stirring speed is 1000r/min, and the stirring time is 25min. And grinding for 2 times to obtain the black paste for the solvent-free polyurethane synthetic leather.
Unlike example 1, comparative example 2 did not add carbon black during the reaction stage, but rather prepared the pre-polymerized polyester polyol first, and the carbon black was not pre-baked to dehydrate, the dispersion process was also a stirred tank with poor sealability, and the preparation method used in comparative example 1 was also a common operation on the current market.
Test experiment
Examples 1-2 and comparative examples 1-2 the ratios of the raw material components in parts by weight are shown in Table 1:
TABLE 1 raw material ratios of examples 1 to 2 and comparative examples 1 to 2
The black pastes for solvent-free polyurethane synthetic leather prepared in examples 1 to 2 and comparative examples 1 to 2 were tested, the pigment particle diameter D97 was tested using a laser particle size distribution meter, the viscosity at normal temperature was tested using a rotational viscometer, the moisture content was tested using a moisture analyzer, the hydroxyl value was tested using a titration analysis method, and the test results are shown in table 2:
table 2: test results of examples 1-2 and comparative examples 1-2
As can be seen from the data in Table 2, the color pastes prepared in examples 1 and 2 are superior to other test samples in terms of particle size, viscosity, moisture content, hydroxyl value and other performance indexes, and are superior to products in the current market.
In conclusion, the black paste for the solvent-free polyurethane synthetic leather has the characteristics of high solid and low viscosity, can meet the coloring requirement, can realize pipeline transportation and online batching, and does not influence the reaction process of the synthetic leather due to low hydroxyl value and low moisture content, so that the peel strength and the wear resistance fastness of the finished leather are not reduced due to the use of the black paste. The finished leather can be used as the improvement of the high-concentration black paste for the common solvent-free polyurethane synthetic leather in the market due to online color matching, and the practicability is strong.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the black paste for the solvent-free polyurethane synthetic leather is characterized by comprising the following steps of:
1) Mixing polyether polyol and carbon black, and then performing pre-drying dehydration to obtain a pre-drying dehydrated material;
2) Adding isophorone diisocyanate and a catalyst into the pre-baked dehydrated material obtained in the step 1) to react to obtain a mixed material;
3) And (3) cooling the mixed material obtained in the step (2), adding a dispersing agent for dispersing, and grinding to obtain the black paste for the solvent-free polyurethane synthetic leather.
2. The method for preparing the black paste for solvent-free polyurethane synthetic leather according to claim 1, wherein the raw materials comprise the following components in parts by weight: 90-110 parts of polyether polyol, 22-32 parts of carbon black, 5-6 parts of isophorone diisocyanate, 0.02-0.03 part of catalyst and 3-6 parts of dispersing agent.
3. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 1 or 2, wherein the polyether polyol comprises a double-ended hydroxyl polyether polyol or a triple-ended hydroxyl polyether polyol.
4. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 3, wherein the dispersing agent comprises organic amine-modified polyurethane, organic amine-modified polyamide or organic amine-modified polyether.
5. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 1, 2 or 4, wherein the catalyst comprises organic bismuth.
6. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 5, wherein the pre-baking and dehydrating temperature in the step 1) is 110-120 ℃ for 30-40 min;
the pre-baking dehydration is carried out under the stirring condition, and the stirring speed is 80-100 r/min.
7. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 1, 2, 4 or 6, wherein the reaction temperature in step 2) is 80-90 ℃ for 120-150 min;
the reaction is carried out under the condition of stirring, and the stirring speed is 100-200 r/min.
8. The method for preparing a black paste for solvent-free polyurethane synthetic leather according to claim 7, wherein the temperature range of the cooling in the step 3) is 40-45 ℃;
the dispersion is carried out under the condition of stirring, the stirring speed is 800-1000 r/min, and the stirring time is 25-30 min;
the grinding times are 2-4 times, and the grinding standard is that the particle size D97 is less than 5 mu m.
9. The black paste for solvent-free polyurethane synthetic leather prepared by the preparation method of any one of claims 1 to 8.
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| CN117285842B (en) * | 2023-11-24 | 2024-02-27 | 黎明化工研究设计院有限责任公司 | Modified color paste, bi-component aromatic polyurethane material and preparation method thereof |
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