CN101445697B - Hyper branched polyurethane leather coating agent and preparation method thereof - Google Patents
Hyper branched polyurethane leather coating agent and preparation method thereof Download PDFInfo
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- CN101445697B CN101445697B CN2008102324300A CN200810232430A CN101445697B CN 101445697 B CN101445697 B CN 101445697B CN 2008102324300 A CN2008102324300 A CN 2008102324300A CN 200810232430 A CN200810232430 A CN 200810232430A CN 101445697 B CN101445697 B CN 101445697B
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Abstract
The invention relates to the technical field of leather coating agents, in particular to a hyper branched polyurethane leather coating agent and a preparation method thereof. The invention aims to solve the problems in the prior art that solvent type polyurethane poses serious potential safety hazard, is apt to pollute the environment, and is manufactured at a high cost. The technical scheme adopted by the invention is that the method for preparing the hyper branched polyurethane leather coating agent comprises the following steps: mixing polyether polylol with isocyanate, stirring to facilitate reaction, adding carboxyl diol as a chain extender for reaction, adding organic amine to neutralize, adding acetone as a solvent for dilution, mixing polyurethane prepolymer with hydroxyl-terminated hyper branched polymer, stirring for reaction, carrying out vacuum pumping, facilitating reaction at a vacuum degree, and recycling acetone. Compared with the prior art, the invention has the advantages that the invention poses no potential safety hazard, is nontoxic and environment-friendly, and is manufactured at a low cost.
Description
Technical field:
The present invention relates to a kind of hide finishes technical field, specially refer to a kind of hyper branched polyurethane leather coating agent and preparation method thereof.
Background technology:
Must carry out surface daub on a wall according to the classification of product through tanning, dyeing, stuffing, dried leather, covering with paint should be satisfied a series of composite request, give the aesthetic feeling of leather height, the color even unanimity, and color and luster is natural, soft; Feel is moistened, and according to different needs wax sense, smooth feeling etc. is arranged; Coating should have firm adhesive property with leather, and is thin and soft and have elasticity, simultaneously good wear resistance, water resisting property should be arranged.Solvent resistance, photostabilization, resistance to deflection, weathering resistance etc.; Coating should have good sanitation performance, and air permeability and good and permeable gas promptly will be arranged.In recent years, urethane (PU) hide finishes has caused the extensive attention of leather circle with its good performance.Polyurethane finishing agent mainly is divided into two classes: solvent borne polyurethane and aqueous polyurethane.Solvent borne polyurethane (solvent-borne type PU) is though stable performance and good physical performance, but contain organic solvent in the present product, therefore product is inflammable, explosive, be difficult for transportation and storage, have serious potential safety hazard, product is poisonous simultaneously, easily contaminate environment, organic solvent causes the cost height in addition, uses to be subjected to certain restriction; And water-based PU is nontoxic, and is energy-conservation, and cost is low, pollution-free, but the too late solvent-borne type PU of physicals, its use range is not as good as solvent borne polyurethane.
Summary of the invention:
The present invention will provide a kind of hyper branched polyurethane leather coating agent and preparation method thereof, with what overcome that existing solvent borne polyurethane exists serious potential safety hazard, easily contaminate environment and the high shortcoming of cost is arranged.
For overcoming the problem that prior art exists, technical scheme of the present invention is: a kind of hyper branched polyurethane leather coating agent, make by following preparation method: at first polyether glycol is mixed by 1: 1～5 mol ratio with isocyanic ester, at 40～100 ℃ of following stirring reaction 60～150min, add 2%～6% carboxylic diol again as chainextender, 30～60 ℃ are reacted 1～3h down, add 2%～6% organic amine neutralization again, add acetone and do solvent cut; At last with base polyurethane prepolymer for use as and superbrnaching end-hydroxy polymkeric substance (1～6 generation) with 1～5: 1 mixed in molar ratio, 40～100 ℃ of following stirring reaction 1～5h, under 40～100 ℃, vacuumize, under the vacuum tightness of 0.02～0.1MPa, react 30～150min, reclaim acetone and get final product.
Above-mentioned polyether glycol is a polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol; Isocyanic ester is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), hexamethylene diisocyanate, hot vulcabond (ODI), the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate (NDI); Carboxylic diol is a dimethylol propionic acid, dimethylolpropionic acid; Organic amine refers to triethylamine, diethylamine.
A kind of preparation method of hyper branched polyurethane leather coating agent: at first a kind of hyper branched polyurethane leather coating agent, this product is made by following preparation method: at first polyether glycol is mixed by 1: 1～5 mol ratio with isocyanic ester, at 40～100 ℃ of following stirring reaction 60～150min, add 2%～6% carboxylic diol again as chainextender, 30～60 ℃ are reacted 1～3h down, add the neutralization of 2%～6% organic amine again, add acetone and do solvent cut; At last with base polyurethane prepolymer for use as and superbrnaching end-hydroxy polymkeric substance (1～6 generation) with 1～5: 1 mixed in molar ratio, 40～100 ℃ of following stirring reaction 1～5h, under 40～100 ℃, vacuumize, under the vacuum tightness of 0.02～0.1MPa, react 30～150min, reclaim acetone and get final product.
Compared with prior art, advantage of the present invention is:
1, no potential safety hazard: in the super branched polyurethane building-up process, because the viscosity of hyperbranched polymer is lower, so it can not only participate in reaction as reactant, can be used as solvent again, thereby reduced the use of (still not using) organic solvent, therefore nonflammable, non-explosive, be easy to transportation and storage.
2, nontoxic, environmental friendliness: do not lack with an organic solvent owing to do not use still, therefore nontoxic still toxicity is little, has the characteristic of high-efficiency environment friendly.
3, cost is low: compare with general polyurethane decorative paint for leather, the hide finishes terminal functionality that this method prepares is big, the reactive behavior height, can with the active group (hydroxyl on leather collagen surface, amino, groups such as carboxyl) combination, form a large amount of firmly chemical bonds, obviously shorten set time, moreover superbrnaching end-hydroxy polymkeric substance (1～6 generation) viscosity is low, with the base polyurethane prepolymer for use as reaction process in, can be not with an organic solvent, the super branched polyurethane that obtains has the overall merit of aqueous polyurethane and solvent borne polyurethane concurrently, has reduced cost.
Description of drawings
Fig. 1 is the building-up reactions synoptic diagram of base polyurethane prepolymer for use as;
Fig. 2 is the building-up reactions synoptic diagram of hyper branched polyurethane leather coating agent.
Specific implementation method:
Referring to accompanying drawing 1 ~ 2 embodiment 1: at first poly(oxyethylene glycol) 400 is mixed by 1: 2 mol ratio with toluene diisocyanate, at 80 ℃ of following stirring reaction 1h, add 3% dimethylol propionic acid again as chainextender, 60 ℃ are reacted 2h down, add massfraction again and be 2.5% triethylamine neutralization, add acetone and do solvent cut.With 1.6: 1 mixed in molar ratio, 80 ℃ of following stirring reaction 4h also reacted 2h under the vacuum tightness of 0.1MPa with this performed polymer and superbrnaching end-hydroxy polymkeric substance (2 generation), reclaimed acetone and got final product.
Referring to accompanying drawing 1 ~ 2 embodiment 2: at first polypropylene glycol 600 is mixed by 1: 2.5 mol ratio with isophorone diisocyanate, at 75 ℃ of following stirring reaction 70min, add 3.5% dimethylol propionic acid again as chainextender, 50 ℃ are reacted 3h down, add massfraction again and be 3% triethylamine neutralization, add acetone and do solvent cut.With 1.8: 1 mixed in molar ratio, 75 ℃ of following stirring reaction 5h also reacted 1h under the vacuum tightness of 0.05MPa with this performed polymer and superbrnaching end-hydroxy polymkeric substance (4 generation), reclaimed acetone and got final product.
Referring to accompanying drawing 1 ~ 2 embodiment 3: at first polypropylene glycol 1000 is mixed by 1: 2.8 mol ratio with tolylene diisocyanate, at 70 ℃ of following stirring reaction 80min, add 4% dimethylolpropionic acid again as chainextender, 55 ℃ are reacted 2.5h down, add massfraction again and be 5% diethylamine neutralization, add acetone and do solvent cut.With 2: 1 mixed in molar ratio, 70 ℃ of following stirring reaction 4.5h also reacted 1.5h under the vacuum tightness of 0.08MPa with this performed polymer and superbrnaching end-hydroxy polymkeric substance (3 generation), reclaimed acetone and got final product.
Referring to accompanying drawing 1 ~ 2 embodiment 4: at first poly(oxyethylene glycol) 400 is mixed by 1: 5 mol ratio with isophorone diisocyanate, at 40 ℃ of following stirring reaction 120min, add 5% dimethylolpropionic acid again as chainextender, 30 ℃ are reacted 3h down, add massfraction again and be 6% triethylamine neutralization, add acetone and do solvent cut.With 5: 1 mixed in molar ratio, 40 ℃ of following stirring reaction 1h also reacted 30min under the vacuum tightness of 0.02MPa with this performed polymer and superbrnaching end-hydroxy polymkeric substance (6 generation), reclaimed acetone and got final product.
Claims (3)
1. hyper branched polyurethane leather coating agent, make by following preparation method: at first polyether glycol is mixed by 1: 1～5 mol ratio with isocyanic ester, at 40～100 ℃ of following stirring reaction 60～150min, add 2%～6% carboxylic diol again as chainextender, 30～60 ℃ are reacted 1～3h down, add the neutralization of 2%～6% organic amine again, add acetone and do solvent cut; At last will by the base polyurethane prepolymer for use as of above-mentioned prepared in reaction and 1～6 generation of superbrnaching end-hydroxy polymkeric substance with 1～5: 1 mixed in molar ratio, 40～100 ℃ of following stirring reaction 1～5h, under 40～100 ℃, vacuumize, under the vacuum tightness of 0.02～0.1MPa, react 30～150min, reclaim acetone and get final product.
2. a kind of hyper branched polyurethane leather coating agent as claimed in claim 1 is characterized in that: described polyether glycol is a polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol; Isocyanic ester is isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), hexamethylene diisocyanate, hot vulcabond (ODI), the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate (NDI); Carboxylic diol is a dimethylol propionic acid, dimethylolpropionic acid; Organic amine refers to triethylamine, diethylamine.
3. the preparation method of a kind of hyper branched polyurethane leather coating agent as claimed in claim 1: at first a kind of hyper branched polyurethane leather coating agent, this product is made by following preparation method: at first polyether glycol is mixed by 1: 1～5 mol ratio with isocyanic ester, at 40～100 ℃ of following stirring reaction 60～150min, add 2%～6% carboxylic diol again as chainextender, 30～60 ℃ are reacted 1～3h down, add the neutralization of 2%～6% organic amine again, add acetone and do solvent cut; At last with base polyurethane prepolymer for use as and 1～6 generation of superbrnaching end-hydroxy polymkeric substance with 1～5: 1 mixed in molar ratio, 40～100 ℃ of following stirring reaction 1～5h, under 40～100 ℃, vacuumize, under the vacuum tightness of 0.02～0.1MPa, react 30～150min, reclaim acetone and get final product.
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| CN2008102324300A CN101445697B (en) | 2008-11-26 | 2008-11-26 | Hyper branched polyurethane leather coating agent and preparation method thereof |
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| CN2008102324300A CN101445697B (en) | 2008-11-26 | 2008-11-26 | Hyper branched polyurethane leather coating agent and preparation method thereof |
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| CN101445697B true CN101445697B (en) | 2011-03-23 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2949478B1 (en) * | 2009-09-03 | 2011-09-02 | Rhodia Poliamida E Especialidades Ltda | LEATHER FINISHING COMPOSITIONS COMPRISING DIOXOLANE DERIVATIVES |
| CN102352011B (en) * | 2011-08-12 | 2013-03-13 | 安徽大学 | Preparation method of aqueous hyperbranched polyurethane |
| CN102493194B (en) * | 2011-12-09 | 2013-12-04 | 陕西科技大学 | Method for modifying superfine fiber synthetic leather based on amino-terminated hyperbranched polymer |
| CN103642952B (en) * | 2013-11-26 | 2015-06-24 | 陕西科技大学 | Method for preparing dendritic-linear polymer fatting agent |
| CN104356354B (en) * | 2014-11-17 | 2017-01-11 | 陕西科技大学 | Preparation method of chromatophilous polyurethane applied to superfine fiber synthetic leather |
| CN105330813B (en) * | 2015-11-03 | 2017-10-20 | 淮安凯悦科技开发有限公司 | A kind of synthetic method of process hides organic silicon modified aqueous polyurethane |
| CN105418887B (en) * | 2015-12-14 | 2018-06-26 | 厦门大邦瑞达印染材料有限公司 | A kind of anionic polyurethane color fixing agent, preparation method and application for acid dyes |
| CN105440259B (en) * | 2015-12-16 | 2018-03-30 | 陕西科技大学 | Using isocyanuric acid ester as hyperbranched aqueous polyurethane of core and preparation method thereof |
| CN106349452B (en) * | 2016-08-19 | 2019-01-25 | 陕西科技大学 | Hold the preparation method of fluoroalkyl super branched polyurethane nano hybridization leather finishing agent |
| 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 |
| CN114292582B (en) * | 2022-01-04 | 2022-07-12 | 江苏苏博特新材料股份有限公司 | Hyperbranched coating suitable for marine concrete, and preparation method and application thereof |
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| CN1385450A (en) * | 2002-04-30 | 2002-12-18 | 上海交通大学 | Branching degree controllable ultrabranching polyurethane and preparation process thereof |
| EP1659140A1 (en) * | 2004-11-18 | 2006-05-24 | HILTI Aktiengesellschaft | Use of hyperbranched polyols for the preparation of polyurethane foams as well as two-component compositions containing them |
| CN1791621A (en) * | 2003-05-16 | 2006-06-21 | 巴斯福股份公司 | Method for producing dendritic or hyperbranched polyurethanes |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385450A (en) * | 2002-04-30 | 2002-12-18 | 上海交通大学 | Branching degree controllable ultrabranching polyurethane and preparation process thereof |
| CN1791621A (en) * | 2003-05-16 | 2006-06-21 | 巴斯福股份公司 | Method for producing dendritic or hyperbranched polyurethanes |
| EP1659140A1 (en) * | 2004-11-18 | 2006-05-24 | HILTI Aktiengesellschaft | Use of hyperbranched polyols for the preparation of polyurethane foams as well as two-component compositions containing them |
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