CN105506997A - Delustering waterborne polyurethane leather finishing agent and preparation method thereof - Google Patents
Delustering waterborne polyurethane leather finishing agent and preparation method thereof Download PDFInfo
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- CN105506997A CN105506997A CN201610055889.2A CN201610055889A CN105506997A CN 105506997 A CN105506997 A CN 105506997A CN 201610055889 A CN201610055889 A CN 201610055889A CN 105506997 A CN105506997 A CN 105506997A
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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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- 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
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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
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
-
- 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
-
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a delustering waterborne polyurethane leather finishing agent and a preparation method thereof. The delustering waterborne polyurethane leather finishing agent is mainly prepared from diisocyanate, polyether glycol, organosiloxane, a hydrophilic chain extender, a catalyst and a neutralizer. According to the delustering waterborne polyurethane leather finishing agent, the specific raw material composition and dosage are adopted, and an excellent delustering effect is obtained without adding a delusterant. The delustering waterborne polyurethane leather finishing agent is good in compactness, stability and coating property, can guarantee the mechanical property and waster resistance of a leather coating and is environmentally friendly, nontoxic and safe. The preparation method of the delustering waterborne polyurethane leather finishing agent is simple in technology, the waterborne polyurethane leather finishing agent with an excellent delustering property is synthesized in a step-by-step feeding reaction mode, and the preparation method is suitable for large-scale production.
Description
Technical field
The present invention relates to leather chemical industry pharmaceutical techniques field, in particular to a kind of extinction type Aqueous Polyurethane Leather Finishing Agent and preparation method thereof.
Background technology
Low luster leather finishing agent is the focus of the research of leather finish now, and artificial synthetic leather can be made apparent closer to corium.
Use delustering agent can reach the extinction effect of expection, but the use of delustering agent can cause the stability of system to decline, and affect the scratch resistance of glued membrane, resistance to bending performance, and additional delustering agent can produce extra cost.And body delustring aqueous polyurethane can overcome above-mentioned defect.
Tradition extinction leather finishing agent mainly adopts the mode of adding silica flatting silica in polyurethane to realize eliminate optical property at present.As patent of invention CN101709550A discloses a kind of leather flatting coating composition and preparation method thereof.It is blended obtained that this antiglossing pigment adopts solvent borne polyurethane and silica dioxide delustring agent to carry out.Solvent based coating environmental pollution is serious on the one hand; On the other hand, silica dioxide delustring agent and the poor compatibility of coating own, easily move out, and affect the performance of polyurethane own.
Patent of invention CN103740250A discloses the preparation method from extinction type leather waterborne polyurethane coating agent.The method has synthesized a kind of polyurethane component A with cross-linked structure greater particle size, and the less B component of itself and particle diameter is mixed.Component A in film forming procedure on float over film surface, make film surface have higher roughness, thus reach extinction effect.This bulky grain component A floats and weakens mechanical property and the water resistance of leather coating to a certain extent.Two component technique for applying is loaded down with trivial details, and if two component mix and unevenly can affect extinction effect.
Patent of invention CN103865031A provides a kind of aqueous polyurethane matting resin, without the need to adding flatting silica, this invention comprises following component: vulcabond 10-18 part, dihydromethyl propionic acid (DMPA) 0.5-5 part, dihydroxylic alcohols 35-60 part, organic bismuth catalyst 0.05-1 part, dimethylethanolamine 0.5-5 part, 2-[(2-aminoethyl) is amino] ethyl sulfonic acid sodium 0.5-10 part, hydrazine hydrate 0.5-5 part, 1-METHYLPYRROLIDONE solvent 1-10 part, deionized water 104-180 part.Product of the present invention, mainly through the chain extension effect of 2-[(2-aminoethyl) amino] ethyl sulfonic acid sodium and hydrazine hydrate, produces coarse emulsion particle, is formed micro-coarse structured when film forming at film surface enrichment, produce extinction effect.But the stability of emulsion on the one hand containing coarse emulsion particle is poor, coarse emulsion particle affects the compactness of emulsion film forming on the other hand, and then affects the serviceability of glued membrane.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is to provide a kind of extinction type Aqueous Polyurethane Leather Finishing Agent, described extinction type Aqueous Polyurethane Leather Finishing Agent has extinction effect excellence, compactness is good, good stability, film is good, mechanical property and the water resistance of leather coating can be ensured, environmental protection, the advantage such as nontoxic, safe.
The second object of the present invention is the preparation method providing a kind of described extinction type Aqueous Polyurethane Leather Finishing Agent, and the method technique is simple, is suitable for large-scale production.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of extinction type Aqueous Polyurethane Leather Finishing Agent, the raw material primarily of following mass fraction prepares:
Vulcabond 13.5-25.5 part, polyether Glycols 8.5-25.3 part, organosiloxane 35.2-72.6 part, hydrophilic chain extender 2.2-6.4 part, catalyst 0.08-0.12 part, neutralizer 1.8-5.2 part;
Be preferably, the raw material primarily of following mass fraction prepares:
Vulcabond 16.5-22.5 part, polyether Glycols 12.7-21.1 part, organosiloxane 45-63.3 part, hydrophilic chain extender 3.3-5.4 part, catalyst 0.09-0.11 part, neutralizer 2.7-4.4 part;
More preferably, the raw material primarily of following mass fraction prepares:
Vulcabond 19.5 parts, polyether Glycols 16.9 parts, organosiloxane 53.9 parts, hydrophilic chain extender 4.3 parts, catalyst 0.1 part, neutralizer 3.5 parts.
Extinction type Aqueous Polyurethane Leather Finishing Agent of the present invention adopts specified raw material composition and consumption, does not need to add delustering agent and just achieves excellent extinction effect; Extinction type Aqueous Polyurethane Leather Finishing Agent compactness of the present invention is good, good stability, and film is good, can ensure mechanical property and the water resistance of leather coating, environmental protection, nontoxic, safety.
Preferably, described vulcabond comprises one or more in toluene di-isocyanate(TDI) (TDI), isoflurane chalcone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), hydrogenation of benzene dicyclohexylmethane diisocyanate (H-MDI) and hexamethylene diisocyanate (HDI); Preferably include in toluene di-isocyanate(TDI) (TDI), isoflurane chalcone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) one or more; Preferably include toluene di-isocyanate(TDI) (TDI) further.
Vulcabond is the speciality chemical that a class has-N=C=O functional group, can be used for manufacturing polyurethane material, adopt specific vulcabond raw material, the extinction type Aqueous Polyurethane Leather Finishing Agent with different eliminate optical property can being prepared, regulating by selecting the eliminate optical property of different vulcabond to gained extinction type Aqueous Polyurethane Leather Finishing Agent; In addition, vulcabond also has certain caking property, can improve mechanical property and the stability of gained extinction type Aqueous Polyurethane Leather Finishing Agent.
Preferably, described polyether Glycols comprises one or more in polyethylene glycol (PEG), polyoxypropyleneglycol (PPG), PTMG (PTMG) and polybutylene glyool adipate (PBA); Preferably include in polyethylene glycol (PEG), polyoxypropyleneglycol (PPG) and PTMG (PTMG) one or more; Preferably include in polyethylene glycol (PEG) and PTMG (PTMG) further one or both.
Polyether Glycols can be used as preparing polyurethane elastomer, coating, adhesive, pavement material etc., adopt specific polyether Glycols raw material, the extinction type Aqueous Polyurethane Leather Finishing Agent with different eliminate optical property can being prepared, regulating by selecting the eliminate optical property of different polyether Glycols to gained extinction type Aqueous Polyurethane Leather Finishing Agent; In addition, polyether Glycols also has certain caking property, can improve mechanical property and the stability of gained extinction type Aqueous Polyurethane Leather Finishing Agent.
Preferably, described organosiloxane comprises one or more in end hydroxypropyl dimethyl silicone polymer, Amino End Group dimethyl silicone polymer and silanol base dimethyl silicone polymer; Preferably include end hydroxypropyl dimethyl silicone polymer and Amino End Group dimethyl silicone polymer in one or more; Preferably include aminopropyl dimethyl silicone polymer further.
Organosiloxane is by the hybrid material formed along inorganic siloxane main chain suspending side organic group, is called as half inorganic polymer.According to the second law of thermodynamics and lang-muir surface action Independence Principle, organosiloxane surface tension is low compared with silica many, and it has following character:
1. surface tension is low, only has fluoropolymer just low than it.
2. characterization pressure is low.
3. there is liquid performance when high molecular.
4. extremely low viscosity-temperature coefficient.
5. hydrophobicity.
Adopt specific organosiloxane, contribute to the stability and the resistance to water that improve gained extinction type Aqueous Polyurethane Leather Finishing Agent, available protecting leather surface.
Preferably, described hydrophilic chain extender comprises one or more of dihydromethyl propionic acid, dihydromethyl propionic acid (DMPA), dimethylolpropionic acid (DMBA) and 2,3-dyhydrobutanedioic acid; Preferably include in dihydromethyl propionic acid (DMPA) and dimethylolpropionic acid (DMBA) one or both; Preferably include dihydromethyl propionic acid (DMPA) further.
Hydrophilic chain extender, also known as hydrophilic chain growing agent, is can make with the functional group reactions on linear polymer chain the material that strand is expanded, molecular weight increases.Adopt specific hydrophilic chain extender effectively can improve mechanical property and the processing performance of gained extinction type Aqueous Polyurethane Leather Finishing Agent.
Preferably, described neutralizer comprises one or more in triethylamine, ammoniacal liquor, NaOH; Preferably include the one in triethylamine and ammoniacal liquor and two kinds; Preferably include triethylamine further.
Adopt specific neutralizer, can improve gained stability of emulsion, gained extinction type Aqueous Polyurethane Leather Finishing Agent is not easy to change in storage and applied at elevated temperature process, and water-resistance property of coating is excellent.
Preferably, described catalyst comprise dibutyl tin laurate (T12), stannous octoate (T9) one or both; Preferably include dibutyl tin laurate (T12).
Adopt special catalyst can promote that polyether Glycols and vulcabond fully react, improve reaction efficiency, improve mechanical property and the processing performance of gained extinction type Aqueous Polyurethane Leather Finishing Agent, and improve eliminate optical property.
Adopt different raw materials can obtain different extinction effects, actual extinction effect regulates by adopting different raw materials and consumption.
The preparation method of above-mentioned a kind of extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
(1) by after polyether Glycols and organosiloxane mixing, at 90-110 DEG C, vacuum stirring is dewatered;
(2) step (1) gained material is cooled to 40-90 DEG C, adds vulcabond and drip catalyst, temperature control, at 70-100 DEG C, reacts 3-6h;
(3) step (2) gained material is cooled to 40-55 DEG C, adds hydrophilic chain extender and solvent, temperature control, at 60-75 DEG C, reacts 1-4h;
(4) step (3) gained material is cooled to 5-15 DEG C, adds neutralizer neutralization, then add water emulsification; Revolve and steam except desolventizing, obtain a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Preparation method's technique of extinction type Aqueous Polyurethane Leather Finishing Agent of the present invention is simple, adopts the mode of Multistep feeding reaction, and synthesis has the Aqueous Polyurethane Leather Finishing Agent of excellent eliminate optical property, is suitable for large-scale production.
Preferably, in described step (1) at 95-105 DEG C, preferred at 100 DEG C further, vacuum stirring is dewatered.
Adopt specified temp, contribute to abundant dehydration, and can promote that material fully mixes.
Preferably, in described step (2), step (1) gained material is cooled to 60-85 DEG C, is preferably cooled to 65 DEG C further.
Preferably, in described step (2), temperature control is at 85-90 DEG C, reaction 3.5-4h, and preferably temperature control, at 85 DEG C, reacts 4h further.
Adopt specified temp, can promote that material fully reacts, improve reaction efficiency, improve mechanical property and the processing performance of gained extinction type Aqueous Polyurethane Leather Finishing Agent, and improve eliminate optical property.
Preferably, described step is cooled to 45-50 DEG C in (3), is preferably cooled to 50 DEG C further.
Preferably, described solvent is acetone.
Preferably, in described step (3), temperature control is at 65-70 DEG C, reaction 2-3h, and preferably temperature control, at 70 DEG C, reacts 3h further.
Adopt specified temp, can promote that material fully reacts, improve reaction efficiency, improve mechanical property and the processing performance of gained extinction type Aqueous Polyurethane Leather Finishing Agent, and improve eliminate optical property.
Preferably, described step is cooled to 10-15 DEG C in (4), is preferably cooled to 10 DEG C further.
Preferably, in described step (4), water is the water bodys such as distilled water, ultra-pure water, deionized water.
Compared with prior art, beneficial effect of the present invention is:
Extinction type Aqueous Polyurethane Leather Finishing Agent of the present invention adopts specified raw material composition and consumption, does not need to add delustering agent and just achieves excellent extinction effect; Extinction type Aqueous Polyurethane Leather Finishing Agent compactness of the present invention is good, good stability, and film is good, can ensure mechanical property and the water resistance of leather coating, environmental protection, nontoxic, safety.Preparation method's technique of extinction type Aqueous Polyurethane Leather Finishing Agent of the present invention is simple, adopts the mode of Multistep feeding reaction, and synthesis has the Aqueous Polyurethane Leather Finishing Agent of excellent eliminate optical property, is suitable for large-scale production.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturer suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Embodiment 1
A preparation method for extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
Weigh 21.632g aminopropyl dimethyl silicone polymer and 10.816gPEG, add in flask, at 100 DEG C, vacuumize 1h, remove moisture.Reduce the temperature to 40 DEG C, add 8.7gTDI and 3 T12, heat up 90 DEG C of reaction 4h.Be cooled to 50 DEG C, add 20g acetone and 2.255gDMPA, be warming up to 70 DEG C, react 2 hours.After temperature is down to about 10 DEG C, product is poured in beaker, under the mixing speed of 1000r/min, add rapidly 1.700g triethylamine and 150.3g water, at the emulsified 5min of 3000r/min rotating speed.Emulsion is steamed removing acetone at 36 DEG C of backspins, obtains a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Embodiment 2
A preparation method for extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
Weigh 26.826g hydroxyl-terminated injecting two methyl siloxane and 6.67gPPG1000, add in flask, at 90 DEG C, vacuumize 2h, remove moisture.Reduce the temperature to 60 DEG C, add 8.433gTDI and 5 T12,85 DEG C of reaction 3h.Be cooled to 45 DEG C, add 30g acetone and 2.3gDMPA, be warming up to 65 DEG C, react 4 hours.After temperature is down to about 5 DEG C, product is poured in beaker, under the mixing speed of 1000r/min, add rapidly 1.734g triethylamine and 153.9g water, at the emulsified 5min of 3000r/min rotating speed.Emulsion is steamed removing acetone at 36 DEG C of backspins, obtains a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Embodiment 3
A preparation method for extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
Weigh 28.91g silanol base dimethyl silicone polymer and 4.818gPTMG, add in flask, at 110 DEG C, vacuumize 1h, remove moisture.Reduce the temperature to 85 DEG C, add 8.242gHDI and 5 T12, reaction 4h.Be cooled to 40 DEG C, add 25g acetone and 2.3gDMPA, be warming up to 65 DEG C, react 4 hours.After temperature is down to about 15 DEG C, product is poured in beaker, under the mixing speed of 1000r/min, add rapidly 1.734g triethylamine and 107.3g water, at the emulsified 5min of 2000r/min rotating speed.Emulsion is steamed removing acetone at 36 DEG C of backspins, obtains a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Embodiment 4
A preparation method for extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
Weigh 21.426g and hold hydroxypropyl silicone oil and 5.356gPEG1000, add in flask, at 90 DEG C, vacuumize 2h, remove moisture.Reduce the temperature to 85 DEG C, add 7.517gTDI and 3 T12, reaction 3.5h.Be cooled to 55 DEG C, add 40g acetone and 2.3gDMPA, be warming up to 70 DEG C, react 3 hours.After temperature is down to about 10 DEG C, product is poured in beaker, under the mixing speed of 1000r/min, add rapidly 0.8g ammonia neutralization and 128.33g water, at the emulsified 5min of 2000r/min rotating speed.Emulsion is steamed removing acetone at 36 DEG C of backspins, obtains a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Embodiment 5
A preparation method for extinction type Aqueous Polyurethane Leather Finishing Agent, comprises the steps:
Weigh 21.42g aminopropyl dimethyl silicone polymer and 5.35gPTMG, add in flask, at 100 DEG C, vacuumize 1h, remove moisture.Reduce the temperature to 90 DEG C, add 9.56gIPDI and 2 T12, reaction 4h.Be cooled to 50 DEG C, add 35g acetone and 2.3gDMPA, be warming up to 75 DEG C, react 2.5 hours.After temperature is down to about 15 DEG C, product is poured in beaker, under the mixing speed of 1000r/min, add rapidly 1.0g ammoniacal liquor and 104.22g water, at the emulsified 5min of 2000r/min rotating speed.Emulsion is steamed removing acetone at 36 DEG C of backspins, obtains a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
Experimental example
Embodiment of the present invention 1-embodiment 5 gained extinction type Aqueous Polyurethane Leather Finishing Agent is carried out outward appearance and eliminate optical property test, acquired results is as shown in table 1:
Table 1 extinction type Aqueous Polyurethane Leather Finishing Agent of the present invention test result
Can be found out, extinction type Aqueous Polyurethane Leather Finishing Agent good stability of the present invention, on the basis of not adding delustering agent composition, to there is excellent eliminate optical property by table 1; In addition, extinction type Aqueous Polyurethane Leather Finishing Agent compactness of the present invention is good, and film is good, can ensure mechanical property and the water resistance of leather coating, environmental protection, nontoxic, safety.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. an extinction type Aqueous Polyurethane Leather Finishing Agent, is characterized in that, the raw material primarily of following mass fraction prepares:
Vulcabond 13.5-25.5 part, polyether Glycols 8.5-25.3 part, organosiloxane 35.2-72.6 part, hydrophilic chain extender 2.2-6.4 part, catalyst 0.08-0.12 part, neutralizer 1.8-5.2 part;
Be preferably, the raw material primarily of following mass fraction prepares:
Vulcabond 16.5-22.5 part, polyether Glycols 12.7-21.1 part, organosiloxane 45-63.3 part, hydrophilic chain extender 3.3-5.4 part, catalyst 0.09-0.11 part, neutralizer 2.7-4.4 part;
More preferably, the raw material primarily of following mass fraction prepares:
Vulcabond 19.5 parts, polyether Glycols 16.9 parts, organosiloxane 53.9 parts, hydrophilic chain extender 4.3 parts, catalyst 0.1 part, neutralizer 3.5 parts.
2. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterized in that, described vulcabond comprise in toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate, methyl diphenylene diisocyanate, hydrogenation of benzene dicyclohexylmethane diisocyanate and hexamethylene diisocyanate one or more; Preferably include in toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate and hexamethylene diisocyanate one or more; Preferably include toluene di-isocyanate(TDI) further.
3. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterized in that, described polyether Glycols comprise in polyethylene glycol, polyoxypropyleneglycol, PTMG and polybutylene glyool adipate one or more; Preferably include in polyethylene glycol, polyoxypropyleneglycol and PTMG one or more; Preferably include in polyethylene glycol and PTMG further one or both.
4. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, it is characterized in that, described organosiloxane comprise in end hydroxypropyl dimethyl silicone polymer, Amino End Group dimethyl silicone polymer and silanol base dimethyl silicone polymer one or more; Preferably include end hydroxypropyl dimethyl silicone polymer and Amino End Group dimethyl silicone polymer in one or more; Preferably include aminopropyl dimethyl silicone polymer further.
5. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, is characterized in that, described hydrophilic chain extender comprises one or more of dihydromethyl propionic acid, dihydromethyl propionic acid, dimethylolpropionic acid and 2,3-dyhydrobutanedioic acid; Preferably include in dihydromethyl propionic acid and dimethylolpropionic acid one or both; Preferably include dihydromethyl propionic acid further.
6. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, is characterized in that, described neutralizer comprise in triethylamine, ammoniacal liquor, NaOH one or more; Preferably include the one in triethylamine and ammoniacal liquor and two kinds; Preferably include triethylamine further.
7. a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 1, is characterized in that, described catalyst comprise dibutyl tin laurate, stannous octoate one or both; Preferably include dibutyl tin laurate.
8. the preparation method of a kind of extinction type Aqueous Polyurethane Leather Finishing Agent as described in as arbitrary in claim 1-7, is characterized in that, comprise the steps:
(1) by after polyether Glycols and organosiloxane mixing, at 90-110 DEG C, vacuum stirring is dewatered;
(2) step (1) gained material is cooled to 40-90 DEG C, adds vulcabond and drip catalyst, temperature control, at 70-100 DEG C, reacts 3-6h;
(3) step (2) gained material is cooled to 40-55 DEG C, adds hydrophilic chain extender and solvent, temperature control, at 60-75 DEG C, reacts 1-4h;
(4) step (3) gained material is cooled to 5-15 DEG C, adds neutralizer neutralization, then add water emulsification; Revolve and steam except desolventizing, obtain a kind of extinction type Aqueous Polyurethane Leather Finishing Agent.
9. the preparation method of a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 8, is characterized in that, in described step (2), temperature control is at 85-90 DEG C, reaction 3.5-4h, and preferred temperature control, at 85 DEG C, reacts 4h.
10. the preparation method of a kind of extinction type Aqueous Polyurethane Leather Finishing Agent according to claim 8, is characterized in that, in described step (3), temperature control is at 65-70 DEG C, reaction 2-3h, and preferred temperature control, at 70 DEG C, reacts 3h.
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| CN106047126A (en) * | 2016-08-10 | 2016-10-26 | 福建宝利特科技股份有限公司 | Leather surface treating agent and processing method thereof |
| CN106244744A (en) * | 2016-08-22 | 2016-12-21 | 福建隆上超纤有限公司 | A kind of modified finishing agent for leather and preparation method thereof |
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