CN105801808A - Synthesis and preparation method for strippable waterborne polyurethane used for leather - Google Patents
Synthesis and preparation method for strippable waterborne polyurethane used for leather Download PDFInfo
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- CN105801808A CN105801808A CN201610019457.6A CN201610019457A CN105801808A CN 105801808 A CN105801808 A CN 105801808A CN 201610019457 A CN201610019457 A CN 201610019457A CN 105801808 A CN105801808 A CN 105801808A
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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
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
- C08G18/58—Epoxy resins
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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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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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
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses strippable waterborne polyurethane used for leather. The strippable waterborne polyurethane is prepared from the following raw materials through multi-step reactions: by mass, 15 to 25 parts of isocyanate, 1 to 10 parts of polyester polyol, 1 to 5 parts of a micromolecule chain extender, 1 to 3 parts of epoxy resin, 1 to 5 parts of a hydrophilic chain extender, 1 to 5 parts of a neutralizing agent, 0 to 3 parts of an amine chain extender, 0.02 to 0.1 part of an organic catalyst, 5 to 15 parts of a cosolvent and 50 to 60 parts of deionized water. The prepared strippable waterborne polyurethane used for the leather provided by the invention has excellent performances like strippability with PET, high brightness, scraping resistance, good recoatability, excellent printability, greenness, environmental protection and low cost, can replace traditional oil-based polyurethane resin to be used as cold-stamping strippable layer type resin, and is extensively applied in the field of cold-stamping printing industry.
Description
Technical field
The invention belongs to film coating production technical field, relate to a kind of synthesis peeling off leather aqueous polyurethane and preparation method.
Background technology
In order to hit various counterfeit and shoddy goods, maintain market stable, various anti-counterfeiting technology fast developments are got up, and cold-hot stamping technology becomes emerging popular anti-counterfeiting technology due to features such as equipment is cheap, plate-making is simple, thermoprint speed is fast, energy-saving and environmental protection, applicable large area thermoprints.Cold-hot stamping technical pattern generally comprises the coating compositions such as PET basement membrane, release layer, dyed layer, aluminium coated, embossed plies (optional), gum layer.Release layer is peel ply, plays buffering PET basement membrane and dyed layer adhesive force effect, for the coating that cold-hot stamping technology is most basic.
Present stage the most frequently used release layer is solvent borne polyurethane coating, although having excellent in stability, heat-resist, jail is combined with aluminium lamination, the advantages such as low price, but there is also defect in printing, apparent brightness, the synthesis of solvent borne polyurethane coating resin needs the use of a large amount of organic solvent in addition, not only contaminated environment, and seriously compromise the health of people.
Patent CN101466754A describes the aqueous urethane resin composition as plastics primer or plastics binding agent, but it adopts the polyamine compounds containing alkoxysilyl as amine chainextender, there is the problem that coating modulus is low, shiny appearance degree is poor, and do not relate to the application in cold wave printing industry field.Patent CN102993405A and CN104530374A describes synthesis and the preparation method of epoxy modified aqueous polyurethane respectively, but it synthesizes this resinoid raw material and is only limited to 2,6-toluene di-isocyanate(TDI)s (TDI).
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, provide a kind of high comprehensive performance, the synthesis of peelable leather aqueous polyurethane and preparation method for cold-hot stamping swabbing industry.
The technical solution used in the present invention is:
A kind of peelable leather aqueous polyurethane, it is characterised in that: it is to be obtained by multistep reaction by the raw material of following mass parts: the isocyanates of 15～25 parts, the PEPA of 1～10 part, the small molecule chain extender of 1～5 part, the epoxy resin of 1～3 part, the hydrophilic chain extender of 1～5 part, the nertralizer of 1～5 part, the amine chainextender of 0～3 part, the organic catalyst of 0.02～0.1 part, the cosolvent of 5～15 parts, the deionized water of 50～60 parts.
Described isocyanates be dicyclohexyl methyl hydride diisocyanate, isoflurane chalcone diisocyanate, 1,6-hexamethylene diisocyanate one or more.
Described PEPA be ethanedioic acid, malonic acid, succinic acid, dimethyl succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, SA, maleic acid and by the materials such as the anhydride of described carboxylic acid derivatives and acid chloride and low-molecular-weight diol such as ethylene glycol, 1; 4 butanediols, diethylene glycol, 1; one or more in the polyester diol that 6-hexanediol, neopentyl glycol etc. are obtained by reacting, the molecular weight of described polyester diol is 300～5000.
Described small molecule chain extender is one or both compounds in ethylene glycol, 1,4 butanediols, diethylene glycol, 1,6-HD, neopentyl glycol.
Described epoxy resin is E-44, or in E-51 one or both.
Described hydrophilic chain extender is 2,2-dihydroxymethyl acetic acid, 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2, the hydrophilic carboxylic acid such as 2-dihydroxymethyl valeric acid and hydrophilic sulfonic acid such as N, N-bis-(the ethoxy)-2-aminoethyl sulfonic acid containing active amino, diaminourea fourth sulfonic acid, 3,6-diaminourea-2-toluenesulfonic acid, 2, one or more in 4-diaminourea-5-toluenesulfonic acid, 1.3-phenylenediamine-4,6-disulfonic acid.
Described nertralizer is at least one in triethylamine, tri-n-butylamine, dimethylethanolamine or ammonia.
Described amine chainextender is one or both compounds in the Diamines such as ethylenediamine, isophorone diamine, 1,3-propane diamine, 1,4-butanediamine, 1,6-hexamethylene diamine, 1,4-cyclohexanediamine.
Described organic catalyst is zinc acetate, manganese acetate, sodium acetate, ammonium acetate, one or more in acetate, triethylene diamine, stannous octoate, dibutyltin dilaurate, two (dodecyl sulfur) dibutyl tin, dibutyltin diacetate, dioctyl tin dilaurate, two (dodecyl sulfur) dioctyl tin, two acetic acid dioctyl tins, the mercaptan dioctyl tin such as potassium acetate, ammonium acetate, calcium acetate.
Described cosolvent is N-Methyl pyrrolidone (NMP), N, one or both compounds in N dimethyl acetamide (DMAC).
The synthesis of peelable leather aqueous polyurethane and preparation method, including step:
1) by PEPA, hydrophilic chain extender, small molecule chain extender and isocyanates, under catalyst action, 80～90 DEG C of reactive polymerics, react 3～3.5h；
2) epoxy resin is added, 80～90 DEG C of reactive polymerics, react 1～2h；
3) mixture in adding, controls temperature 45～55 DEG C, neutralizes 0.5～1h；
4) adding deionized water emulsifying, mixing speed is 500～2000rpm, and the time is 30min；
5) adding amine chainextender, mixing speed is 500～1000rpm, is incubated 1～3h,.
The invention has the beneficial effects as follows: adopt epoxy resin modification base polyurethane prepolymer for use as, aqueous polyurethane stability, temperature tolerance, resistance to scraping and modulus can not only be greatly improved, solve oil product printing not good, the defects such as apparent brightness difference, and its replace conventional oil-based polyurethane resin be used as cold-hot stamping release layer time, make product more preferably environmental protection, reduce production cost simultaneously.
Detailed description of the invention
A kind of peelable leather aqueous polyurethane, it is characterised in that: it is to be obtained by multistep reaction by the raw material of following mass parts: the isocyanates of 15～25 parts, the PEPA of 1～10 part, the small molecule chain extender of 1～5 part, the epoxy resin of 1～3 part, the hydrophilic chain extender of 1～5 part, the nertralizer of 1～5 part, the amine chainextender of 0～3 part, the organic catalyst of 0.02～0.1 part, the cosolvent of 5～15 parts, the deionized water of 50～60 parts.
Described isocyanates be dicyclohexyl methyl hydride diisocyanate, isoflurane chalcone diisocyanate, 1,6-hexamethylene diisocyanate one or more.
Described PEPA be ethanedioic acid, malonic acid, succinic acid, dimethyl succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, SA, maleic acid and by the materials such as the anhydride of described carboxylic acid derivatives and acid chloride and low-molecular-weight diol such as ethylene glycol, 1; 4 butanediols, diethylene glycol, 1; one or more in the polyester diol that 6-hexanediol, neopentyl glycol etc. are obtained by reacting, the molecular weight of described polyester diol is 300～5000.
Preferably, the molecular weight of described polyester diol is 1000～3000.
Described small molecule chain extender is one or both compounds in ethylene glycol, 1,4 butanediols, diethylene glycol, 1,6-HD, neopentyl glycol.
Described epoxy resin is E-44, or in E-51 one or both.
Described hydrophilic chain extender is 2,2-dihydroxymethyl acetic acid, 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2, the hydrophilic carboxylic acid such as 2-dihydroxymethyl valeric acid and hydrophilic sulfonic acid such as N, N-bis-(the ethoxy)-2-aminoethyl sulfonic acid containing active amino, diaminourea fourth sulfonic acid, 3,6-diaminourea-2-toluenesulfonic acid, 2, one or more in 4-diaminourea-5-toluenesulfonic acid, 1.3-phenylenediamine-4,6-disulfonic acid.
Described nertralizer is at least one in triethylamine, tri-n-butylamine, dimethylethanolamine or ammonia.
Described amine chainextender is one or both compounds in the Diamines such as ethylenediamine, isophorone diamine, 1,3-propane diamine, 1,4-butanediamine, 1,6-hexamethylene diamine, 1,4-cyclohexanediamine.
Preferably, described amine chainextender is one or both compounds in ethylenediamine, isophorone diamine.
Described organic catalyst is zinc acetate, manganese acetate, sodium acetate, ammonium acetate, one or more in acetate, triethylene diamine, stannous octoate, dibutyltin dilaurate, two (dodecyl sulfur) dibutyl tin, dibutyltin diacetate, dioctyl tin dilaurate, two (dodecyl sulfur) dioctyl tin, two acetic acid dioctyl tins, the mercaptan dioctyl tin such as potassium acetate, ammonium acetate, calcium acetate.
Preferably, described organic catalyst is one or more in triethylene diamine, stannous octoate, dibutyltin dilaurate, two (dodecyl sulfur) dibutyl tin, dibutyltin diacetate, dioctyl tin dilaurate, two (dodecyl sulfur) dioctyl tin, two acetic acid dioctyl tins, mercaptan dioctyl tin.
Described cosolvent is N-Methyl pyrrolidone (NMP), N, one or both compounds in N dimethyl acetamide (DMAC).
The synthesis of peelable leather aqueous polyurethane and preparation method, including step:
1) by PEPA, hydrophilic chain extender, small molecule chain extender and isocyanates, under catalyst action, 80～90 DEG C of reactive polymerics, react 3～3.5h；
2) epoxy resin is added, 80～90 DEG C of reactive polymerics, react 1～2h；
3) mixture in adding, controls temperature 45～55 DEG C, neutralizes 0.5～1h；
4) adding deionized water emulsifying, mixing speed is 500～2000rpm, and the time is 30min；
5) adding amine chainextender, mixing speed is 500～1000rpm, is incubated 1～3h,.
Below in conjunction with specific embodiment, the synthesis of the peelable leather aqueous polyurethane of the present invention is described further with preparation method:
Embodiment 1:
Equipped with agitator, thermometer, reflux condensing tube dry reaction still in, add 5 parts of PEPAs, 3 parts of hydrophilic chain extenders (dihydromethyl propionic acid), 3 parts of small molecule chain extenders (1,4-butanediol), 17 parts of isoflurane chalcone diisocyanates and 8 parts of cosolvents (NMP), under 0.02 part of catalyst (stannous octoate) effect, 80 DEG C of reactive polymerics, react 3h；It is subsequently adding 1 part of epoxy resin E-44, continues reaction 1.5h in 80 DEG C；It is cooled to 50 DEG C, adds the nertralizer triethylamine with dihydromethyl propionic acid equimolar amounts, neutralize 0.5h；Adding 59 parts of deionized water emulsifyings of people, mixing speed is 800rpm, and the time is 30min；Adding 1 part of chain extender (isophorone diamine), mixing speed is 500rpm, is incubated 2h at 50 DEG C.Thus obtaining the strippable waterborne polyurethane resin of a kind of high comprehensive performance.Opening rare by a certain percentage by above-mentioned emulsion ethanol and water, Gu containing being diluted to 1.5%, be coated with on PET, coating dry measure is 0.07g/m2, most high dry temperature is 150 DEG C, after drying and forming-film, obtains required figure layer.
Embodiment 2:
Equipped with agitator, thermometer, reflux condensing tube dry reaction still in, add 3 parts of PEPAs, 4 parts of hydrophilic chain extenders (dihydromethyl propionic acid), 3.5 parts of small molecule chain extenders (1,4-butanediol), 20 parts of isoflurane chalcone diisocyanates and 10 parts of cosolvents (NMP), under 0.02 part of catalyst (stannous octoate) effect, 80 DEG C of reactive polymerics, react 3h；It is subsequently adding 1 part of epoxy resin E-44, continues reaction 2h in 80 DEG C；It is cooled to 55 DEG C, adds the nertralizer triethylamine with dihydromethyl propionic acid equimolar amounts, neutralize 0.5h；Adding 53.5 parts of deionized water emulsifyings of people, mixing speed is 1000rpm, and the time is 30min；Adding 1 part of chain extender (isophorone diamine), mixing speed is 800rpm, is incubated 2.5h at 50 DEG C.Thus obtaining the strippable waterborne polyurethane resin of a kind of high comprehensive performance.Opening rare by a certain percentage by above-mentioned emulsion ethanol and water, Gu containing being diluted to 2%, be coated with on PET, coating dry measure is 0.075g/m2, most high dry temperature is 150 DEG C, after drying and forming-film, obtains required figure layer.
Embodiment 3:
Equipped with agitator, thermometer, reflux condensing tube dry reaction still in, add 7 parts of PEPAs, 3 parts of hydrophilic chain extenders (dihydromethyl propionic acid), 2 parts of small molecule chain extenders (1,4-butanediol), 15 parts of isoflurane chalcone diisocyanates and 12 parts of cosolvents (NMP), under 0.02 part of catalyst (stannous octoate) effect, 80 DEG C of reactive polymerics, react 3h；It is subsequently adding 1.5 parts of epoxy resin E-51, continues reaction 2h in 80 DEG C；It is cooled to 50 DEG C, adds the nertralizer triethylamine with dihydromethyl propionic acid equimolar amounts, neutralize 0.5h；Adding 55.5 parts of deionized water emulsifyings of people, mixing speed is 1500rpm, and the time is 30min；Adding 1.5 parts of chain extenders (isophorone diamine), mixing speed is 800rpm, is incubated 2h at 50 DEG C.Thus obtaining the strippable waterborne polyurethane resin of a kind of high comprehensive performance.Opening rare by a certain percentage by above-mentioned emulsion ethanol and water, Gu containing being diluted to 2.5%, be coated with on PET, coating dry measure is 0.09g/m2, most high dry temperature is 150 DEG C, after drying and forming-film, obtains required figure layer.
Embodiment 1～3 is obtained product and carries out gloss appearance degree (the glossiness tester test that Shanghai Pu Shen chemical machinery company limited produces), peeling force (the TestingMachines test that TMI company produces), solvent resistance (ethanol) (according to GB/T23989-2009 " coating solvent resistant wiping method of testing " test), VOC content (according to HJ/T201-2005 " People's Republic of China's environmental conservation industry standard ") and surface can be detected in (the dyne pen test that Pacific Co., Ltd produces), related data is listed in table 1 respectively, wherein, reduced value is the test value of oiliness sample.
Table 1: prepare the performance data table of product in embodiment 1～3
| Pilot project title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Oiliness sample |
| Gloss appearance degree | 185 | 168 | 171 | 105 |
| Peeling force (gf) | 9 | 11 | 12 | 12 |
| Solvent resistance (ethanol) | Pass through | Pass through | Pass through | Pass through |
| VOC content | Pass through | Pass through | Pass through | Exceed standard |
| Surface energy (dyne) | 48 | 48 | 48 | 42 |
From table 1 it follows that the present invention is suitable with oil product in the performance such as peeling force, solvent resistance, but can there is obvious advantage on glossiness, surface, and also can safety VOC detection.
Claims (11)
1. a peelable leather aqueous polyurethane, it is characterised in that: it is to be obtained by multistep reaction by the raw material of following mass parts: the isocyanates of 15～25 parts, the PEPA of 1～10 part, the small molecule chain extender of 1～5 part, the epoxy resin of 1～3 part, the hydrophilic chain extender of 1～5 part, the nertralizer of 1～5 part, the amine chainextender of 0～3 part, the organic catalyst of 0.02～0.1 part, the cosolvent of 5～15 parts, the deionized water of 50～60 parts.
2. the peelable leather aqueous polyurethane of one according to claim 1, it is characterised in that: described isocyanates be dicyclohexyl methyl hydride diisocyanate, isoflurane chalcone diisocyanate, 1,6-hexamethylene diisocyanate one or more.
3. the peelable leather aqueous polyurethane of one according to claim 1; it is characterized in that: described PEPA be ethanedioic acid, malonic acid, succinic acid, dimethyl succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, SA, maleic acid and by the materials such as the anhydride of described carboxylic acid derivatives and acid chloride and low-molecular-weight diol such as ethylene glycol, 1; 4 butanediols, diethylene glycol, 1; one or more in the polyester diol that 6-hexanediol, neopentyl glycol etc. are obtained by reacting, the molecular weight of described polyester diol is 300～5000.
4. the peelable leather aqueous polyurethane of one according to claim 1, it is characterised in that: described small molecule chain extender is one or both compounds in ethylene glycol, Isosorbide-5-Nitrae butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol.
5. the peelable leather aqueous polyurethane of one according to claim 1, it is characterised in that: described epoxy resin is E-44, or in E-51 one or both.
6. the peelable leather aqueous polyurethane of one according to claim 5, it is characterized in that: described hydrophilic chain extender is 2,2-dihydroxymethyl acetic acid, 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid, 2, the hydrophilic carboxylic acid such as 2-dihydroxymethyl valeric acid and the hydrophilic sulfonic acid such as N containing active amino, N-bis-(ethoxy)-2-aminoethyl sulfonic acid, diaminourea fourth sulfonic acid, 3,6-diaminourea-2-toluenesulfonic acid, 2,4-diaminourea-5-toluenesulfonic acid, 1.3-phenylenediamine-4, one or more in 6-disulfonic acid.
7. the peelable leather aqueous polyurethane of one according to claim 1, it is characterised in that: described nertralizer is at least one in triethylamine, tri-n-butylamine, dimethylethanolamine or ammonia.
8. the peelable leather aqueous polyurethane of one according to claim 1, it is characterized in that: described amine chainextender be ethylenediamine, isophorone diamine, 1,3-propane diamine, Putriscine, 1, one or both compounds in the Diamines such as 6-hexamethylene diamine, Isosorbide-5-Nitrae-cyclohexanediamine.
9. the peelable leather aqueous polyurethane of one according to claim 1, it is characterized in that: described organic catalyst is zinc acetate, manganese acetate, sodium acetate, ammonium acetate, one or more in acetate, triethylene diamine, stannous octoate, dibutyltin dilaurate, two (dodecyl sulfur) dibutyl tin, dibutyltin diacetate, dioctyl tin dilaurate, two (dodecyl sulfur) dioctyl tin, two acetic acid dioctyl tins, the mercaptan dioctyl tin such as potassium acetate, ammonium acetate, calcium acetate.
10. the peelable leather aqueous polyurethane of one according to claim 1, it is characterised in that: described cosolvent is N-Methyl pyrrolidone (NMP), N, one or both compounds in N dimethyl acetamide (DMAC).
11. the synthesis of a kind of peelable leather aqueous polyurethane described in claim 1 and preparation method, it is characterised in that: include step:
1) by PEPA, PEPA cross-linking agent, hydrophilic chain extender, small molecule chain extender and isocyanates, under catalyst action, 80～90 DEG C of reactive polymerics, react 3～3.5h；
2) epoxy resin is added, 80～90 DEG C of reactive polymerics, react 1～2h；
3) mixture in adding, controls temperature 45～55 DEG C, neutralizes 0.5～1h；
4) adding deionized water emulsifying, mixing speed is 500～2000rpm, and the time is 30min；
5) adding amine chainextender, mixing speed is 500～1000rpm, is incubated 1～3h,.
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| CN113956431A (en) * | 2021-12-06 | 2022-01-21 | 南雄西顿化工有限公司 | Waterborne polyurethane for woodware with high alcohol resistance and preparation method thereof |
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| CN109021906A (en) * | 2018-06-11 | 2018-12-18 | 合肥安利聚氨酯新材料有限公司 | A kind of soccerballleather solventless polyurethane adhesive layer resin and the preparation method and application thereof |
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| CN109535384A (en) * | 2018-11-19 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous polyurethane emulsion and preparation method thereof and vacuum plastic-absorption |
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