CN104193941A - Hyperbranched non-ionic waterborne polyurethane leather finishing agent and preparation method thereof - Google Patents

Hyperbranched non-ionic waterborne polyurethane leather finishing agent and preparation method thereof Download PDF

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Publication number
CN104193941A
CN104193941A CN201410467668.7A CN201410467668A CN104193941A CN 104193941 A CN104193941 A CN 104193941A CN 201410467668 A CN201410467668 A CN 201410467668A CN 104193941 A CN104193941 A CN 104193941A
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hyperbranched
hide finishes
add
polyurethane
diol
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CN104193941B (en
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黄凯
孙海园
刘娅林
马金明
闫克辉
陈建栋
王铁森
陈玉国
于福哲
苗吉宾
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SHANDONG TIANQING TECHNOLOGY DEVELOPMENT Co Ltd
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SHANDONG TIANQING TECHNOLOGY DEVELOPMENT Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3834Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/61Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates 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
    • C08G18/753Polyisocyanates 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
    • C08G18/755Polyisocyanates 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

Abstract

The invention provides a hyperbranched non-ionic waterborne polyurethane leather finishing agent and a preparation method thereof. The leather finishing agent is mainly prepared from raw materials, such as oligomer polyhydric alcohol, isocyanate, polysiloxane, trimethylolpropane polyethylene glycol monomethyl ether and terminal hydroxyl hyperbranched polymers. The leather finishing agent is high in solid content, high in water resistance and high in chemical stability for electrolyte.

Description

Hyperbranched non-ion aqueous polyurethane hide finishes and preparation method thereof
Technical field
The invention belongs to chemical technology field, particularly a kind of non-ion aqueous polyurethane hide finishes and preparation method thereof.
Background technology
The most of internal emulsification method that uses of existing ionic polyurethanes is in emulsifying polyurethane and water, when wetting ability chainextender uses when less, and emulsification difficulty, and polyurethane particles is larger, less stable, and product film forming outward appearance is poor; When wetting ability chainextender uses when more, when film forming, water tolerance is poor.Because the urethane of preparation is ionic polyurethanes, to ionogen sensitivity, make the compatibleness of polyurethane products and other ionic polyurethanes and various auxiliary agents poor, stability is low, is unfavorable for standing storage.
Hyperbranched polymer (hyperbranched polymer) is the polymkeric substance of the special macromolecular structure that grows up recent years, of common occurrence in the application aspect the covering with paint of the functional materialss such as leather, synthetic leather, luminescent material and nano material about hyperbranched polymer.In recent years, hyperbranched polymer due to its have highly branched three-dimensional structure and a large amount of end group group with and demonstrate the extensive concern that causes leather circle from the many different premium propertiess of linear polymeric.
Summary of the invention
The invention provides a kind of hyperbranched non-ion aqueous polyurethane hide finishes and preparation method thereof, to overcome, the solid content that existing ionic polyurethanes exists is low, poor water resistance and the shortcoming to ionogen sensitivity.
Hyperbranched non-ion aqueous polyurethane hide finishes of the present invention, is mainly prepared from by the raw material of following parts by weight: oligomer polyol 22.3-62.5 part, isocyanic ester 18-36 part, polysiloxane 1.2-3.6 part, TriMethylolPropane(TMP) poly glycol monomethyl ether 2.4-19.1 part, hydroxy diol 1.2-2 part, catalyzer 0.03-0.07 part, deionized water 102-205 part, alkanolamine 0.8-4.3 part, Hyperbranched Polymer with Terminal Hydroxyl 8.3-32.6 part, adipic dihydrazide linking agent 0.2-2 part.
According to the present invention, it is 2000 that described oligomer polyol is selected from molecular weight, and hydroxyl value is the polytetramethylene ether diol of 55-60 KOH mg/g; Molecular weight is 2000, and hydroxyl value is the PTMG of 55-60 KOH mg/g; Molecular weight is 2000, and hydroxyl value is the one in the polycarbonate diol of 55-60 KOH mg/g.
Described isocyanic ester is selected from tolylene diisocyanate (TDI), benzhydryl vulcabond (MDI), isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate, pungent vulcabond (ODI), the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate (NDI), hexahydrotoluene vulcabond.
Described catalyzer is stannous octoate.
Described hydroxy diol is selected from BDO, 1,6-hexylene glycol, neopentyl glycol.
Described Hyperbranched Polymer with Terminal Hydroxyl is hyper-branched polyester Boltorn H40.
Boltorn H40 is commercial goods.
Described alkanolamine is triethylamine, dimethylaminoethanol.
The preparation method of hyperbranched non-ion aqueous polyurethane hide finishes of the present invention, mainly comprises the steps:
First oligomer polyol is mixed with isocyanic ester, at 60-100 DEG C of stirring reaction 60-180 min, add again polysiloxane to obtain performed polymer by step-reaction polymerization, add TriMethylolPropane(TMP) poly glycol monomethyl ether, hydroxy diol and catalyzer, after 50-80 DEG C of reaction 30-90 min, add non-proton organic solvent to regulate viscosity to 70-80 mPa.s, being cooled to 50-70 DEG C slowly adds Hyperbranched Polymer with Terminal Hydroxyl to continue to stir 30-90 min, maintain viscosity to 70-80 mPa.s with non-proton organic solvent during this time, make urethane intermediate product, under agitation will in the frozen water of join with alkanolamine-10-0 of urethane intermediate product DEG C, mix ,-10-0 DEG C of stirring reaction, stirs 30-120 min and makes polyurethane aqueous dispersion body, in polyurethane aqueous dispersion body, add adipic dihydrazide linking agent stirring reaction 10-30min, obtain milky hyperbranched non-ion aqueous polyurethane emulsion.
According to the present invention, described non-proton organic solvent is selected from acetone, methylethylketone or N, N-dimethyl pyrrolidone.
Compared with prior art, hide finishes of the present invention has following advantage:
1, solid content is high: in super branched polyurethane building-up process, owing to having introduced dissaving structure polymkeric substance, the solid content of product is improved;
2, water tolerance is strong: by the introducing of organosilicon function monomer, organosilicon is combined with polyurethane chemistry, adds adipic dihydrazide linking agent preparing in polyurethane aqueous dispersion body, make product self-crosslinking in film process, improved the water tolerance of film, water-intake rate is obviously better than conventional polyurethanes;
3, high to electrolytical chemical stability: owing to having used non-ionic hydrophilic chainextender, to make polyurethane aqueous dispersion have good chemical stability to electrolyte solution.
Brief description of the drawings
Fig. 1 is the synthetic schematic diagram of base polyurethane prepolymer for use as;
Fig. 2 is the synthetic schematic diagram of hyperbranched non-ion aqueous polyurethane.
Embodiment
Embodiment 1
Referring to accompanying drawing 1-2, first by 62.5 kg PTMG (PTMG, Mn=2000, hydroxyl value=57.4 KOH mg/g) mix with 22 kg isoflurane chalcone diisocyanates, at 80 DEG C of stirring reaction 180 min, add again 1.7 g polysiloxane (gushing strange FS6098) to obtain base polyurethane prepolymer for use as by step-reaction polymerization, add 4 kg TriMethylolPropane(TMP) macrogol monomethyl ethers and 1.2 kg dimethylol propionic acids as chainextender, 0.03 g stannous octoate catalyst, after 70 DEG C of reaction 90 min, add acetone to regulate viscosity to 70-80 mPa.s, be cooled to 50 DEG C and slowly add the 12.5 Boltorn H40 of Bai Situo company of kg hyper-branched polyester Boltorn H40(Sweden) continuation stirring 60 min, maintain viscosity to 70-80 mPa.s with non-proton organic solvent during this time, make urethane intermediate product, under high shear force (rotating speed is controlled at 1000-2000r/min), intermediate product and 0.8 kg dimethylaminoethanol are joined in 205 kg frozen water (temperature-10 DEG C), low-temperature mixed, the polyurethane aqueous dispersion body of making after-5 DEG C of stirring reaction 60min, add 0.4 kg adipic dihydrazide linking agent stirring reaction 10min preparing in polyurethane aqueous dispersion body, obtain milky hyperbranched non-ion aqueous polyurethane emulsion.
Embodiment 2
Referring to accompanying drawing 1-2, first by 53.6 kg PTMG (PTMG, Mn=2000, hydroxyl value=57.4 KOH mg/g) mix with 36 kg isoflurane chalcone diisocyanates, at 70 DEG C of stirring reaction 180 min, add again 2.6 g polysiloxane (gushing strange FS6098) to obtain base polyurethane prepolymer for use as by step-reaction polymerization, add 6 kg TriMethylolPropane(TMP) macrogol monomethyl ethers and 1.6 kg dimethylol propionic acids as chainextender, 0.06 g stannous octoate catalyst, after 70 DEG C of reaction 90 min, add acetone to regulate viscosity to 70-80 mPa.s, be cooled to 50 DEG C and slowly add the 10.8 Boltorn H40 of Bai Situo company of kg hyper-branched polyester Boltorn H40(Sweden) continuation stirring 60 min, maintain viscosity to 70-80 mPa.s with non-proton organic solvent during this time, make urethane intermediate product, under high shear force (rotating speed is controlled at 1000-2000r/min), intermediate product and 1.06 kg dimethylaminoethanols are joined in 200 kg frozen water (temperature-5 DEG C), low-temperature mixed, the polyurethane aqueous dispersion body of making after-5 DEG C of stirring reaction 60min, add 0.6 kg adipic dihydrazide linking agent stirring reaction 10min preparing in polyurethane aqueous dispersion body, obtain milky hyperbranched non-ion aqueous polyurethane emulsion.
Embodiment 3
Referring to accompanying drawing 1-2, first by 58.2 kg polytetramethylene ether diol (Mn=2000, hydroxyl value=57.4 KOH mg/g) mix with 27 kg isoflurane chalcone diisocyanates, at 80 DEG C of stirring reaction 180 min, add again 2.1 g polysiloxane (gushing strange FS6098) to obtain base polyurethane prepolymer for use as by step-reaction polymerization, add 8 kg TriMethylolPropane(TMP) macrogol monomethyl ethers and 2 kg dimethylol propionic acids as chainextender, 0.03 g stannous octoate catalyst, after 70 DEG C of reaction 90 min, add acetone to regulate viscosity to 70-80 mPa.s, be cooled to 50 DEG C and slowly add the 7.9 Boltorn H40 of Bai Situo company of kg hyper-branched polyester Boltorn H40(Sweden) continuation stirring 60 min, maintain viscosity to 70-80 mPa.s with non-proton organic solvent during this time, make urethane intermediate product, under high shear force (rotating speed is controlled at 1000-2000r/min), intermediate product and 1.3 kg dimethylaminoethanols are joined in 195 kg frozen water (temperature-10 DEG C), low-temperature mixed, the polyurethane aqueous dispersion body of making after-5 DEG C of stirring reaction 60min, add 0.6 kg adipic dihydrazide linking agent stirring reaction 10min preparing in polyurethane aqueous dispersion body, obtain milky hyperbranched non-ion aqueous polyurethane emulsion.

Claims (9)

1. a hyperbranched non-ion aqueous polyurethane hide finishes, it is characterized in that, be mainly prepared from by the raw material of following parts by weight: oligomer polyol 22.3-62.5 part, isocyanic ester 18-36 part, polysiloxane 1.2-3.6 part, TriMethylolPropane(TMP) poly glycol monomethyl ether 2.4-19.1 part, hydroxy diol 1.2-2 part, catalyzer 0.03-0.07 part, deionized water 102-205 part, alkanolamine 0.8-4.3 part, Hyperbranched Polymer with Terminal Hydroxyl 8.3-32.6 part, adipic dihydrazide linking agent 0.2-2 part.
2. hide finishes as claimed in claim 1, is characterized in that, it is 2000 that described oligomer polyol is selected from molecular weight, and hydroxyl value is the polytetramethylene ether diol of 55-60 KOH mg/g; Molecular weight is 2000, and hydroxyl value is the PTMG of 55-60 KOH mg/g; Molecular weight is 2000, and hydroxyl value is the one in the polycarbonate diol of 55-60 KOH mg/g.
3. hide finishes as claimed in claim 1, it is characterized in that, described isocyanic ester is selected from tolylene diisocyanate (TDI), benzhydryl vulcabond (MDI), isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate, pungent vulcabond (ODI), the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate (NDI), hexahydrotoluene vulcabond.
4. hide finishes as claimed in claim 1, is characterized in that, described catalyzer is stannous octoate.
5. hide finishes as claimed in claim 1, is characterized in that, described hydroxy diol is selected from BDO, 1,6-hexylene glycol, neopentyl glycol.
6. hide finishes as claimed in claim 1, is characterized in that, described Hyperbranched Polymer with Terminal Hydroxyl is hyper-branched polyester Boltorn H40.
7. hide finishes as claimed in claim 1, is characterized in that, described alkanolamine is triethylamine, dimethylaminoethanol.
8. the preparation method of hyperbranched non-ion aqueous polyurethane hide finishes as described in claim 1-7 any one, is characterized in that, mainly comprises the steps:
First oligomer polyol is mixed with isocyanic ester, at 60-100 DEG C of stirring reaction 60-180 min, add again polysiloxane to obtain performed polymer by step-reaction polymerization, add TriMethylolPropane(TMP) poly glycol monomethyl ether, hydroxy diol and catalyzer, after 50-80 DEG C of reaction 30-90 min, add non-proton organic solvent to regulate viscosity to 70-80 mPa.s, being cooled to 50-70 DEG C slowly adds Hyperbranched Polymer with Terminal Hydroxyl to continue to stir 30-90 min, maintain viscosity to 70-80 mPa.s with non-proton organic solvent during this time, make urethane intermediate product, under agitation will in the frozen water of join with alkanolamine-10-0 of urethane intermediate product DEG C, mix ,-10-0 DEG C of stirring reaction, stirs 30-120 min and makes polyurethane aqueous dispersion body, in polyurethane aqueous dispersion body, add adipic dihydrazide linking agent stirring reaction 10-30min, obtain milky hyperbranched non-ion aqueous polyurethane emulsion.
9. preparation method as claimed in claim 8, is characterized in that, described non-proton organic solvent is selected from acetone, methylethylketone or N, N-dimethyl pyrrolidone.
CN201410467668.7A 2014-09-15 2014-09-15 Hyperbranched non-ion aqueous polyurethane leather finishing agent and preparation method thereof Active CN104193941B (en)

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Cited By (9)

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CN104926216A (en) * 2015-06-15 2015-09-23 洛阳理工学院 Preparation method of thermal-insulation building material
CN106916277A (en) * 2017-04-18 2017-07-04 中国科学院长春应用化学研究所 A kind of organic-silicon-modified cation aqueous polyurethane and preparation method thereof
CN107033320A (en) * 2017-03-31 2017-08-11 优美特(北京)环境材料科技股份公司 Hydroxyl water-borne dispersions and preparation method thereof
CN108752563A (en) * 2018-05-24 2018-11-06 哈尔滨工业大学无锡新材料研究院 Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition
CN109535377A (en) * 2018-12-04 2019-03-29 山东天庆科技发展有限公司 A kind of aqueous polyurethane and the preparation method and application thereof with from foam stabilizing function
WO2021103376A1 (en) * 2019-11-26 2021-06-03 齐河力厚化工有限公司 Non-ionic waterborne polyurethane, preparation method therefor and application thereof
US11254991B2 (en) * 2019-07-09 2022-02-22 Lear Corporation Use of non-ionically stabilized waterborne antisoil coatings for automotive leather
CN116004107A (en) * 2022-12-27 2023-04-25 广州集泰化工股份有限公司 3C water-based paint and preparation method and application thereof
US11976158B2 (en) 2019-11-26 2024-05-07 Qihe Leahou Chemical Co., Ltd. Non-ionic water based polyurethane and preparation method and use thereof

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WO2013020820A1 (en) * 2011-08-05 2013-02-14 Basf Se Associative thickeners based on hyperbranched polymers
CN103450837A (en) * 2013-09-03 2013-12-18 山东天庆科技发展有限公司 Waterborne polyurethane adhesive for synthetic leather and preparation method thereof

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CN101481578A (en) * 2009-02-03 2009-07-15 广州慧谷化学有限公司 Capacitor coating with deep drawing resistant performance and high temperature yellowing resistance and preparation thereof
WO2013020820A1 (en) * 2011-08-05 2013-02-14 Basf Se Associative thickeners based on hyperbranched polymers
CN103450837A (en) * 2013-09-03 2013-12-18 山东天庆科技发展有限公司 Waterborne polyurethane adhesive for synthetic leather and preparation method thereof

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