CN111269388A - Production method of high-yield waterborne polyurethane environment-friendly resin - Google Patents
Production method of high-yield waterborne polyurethane environment-friendly resin Download PDFInfo
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- CN111269388A CN111269388A CN202010242832.XA CN202010242832A CN111269388A CN 111269388 A CN111269388 A CN 111269388A CN 202010242832 A CN202010242832 A CN 202010242832A CN 111269388 A CN111269388 A CN 111269388A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/66—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
- 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
Abstract
The invention discloses a high-yield waterborne polyurethane environment-friendly resin which comprises the following materials: the production steps of the waterborne polyurethane resin comprise the steps of taking the polyester polyol, the cyanate ester and the toluene diisocyanate out, sequentially adding the polyester polyol, the cyanate ester and the toluene diisocyanate into a reaction kettle according to a proportion, carrying out addition reaction for a period of time at a certain temperature, then respectively carrying out prepolymerization reaction, chain extension reaction and neutralization reaction, and finally carrying out high-speed stirring and emulsification treatment to obtain the stable waterborne polyurethane resin. The production process adopts a prepolymer method to produce the waterborne polyurethane resin, and has the characteristics of simple process, low cost, and compared with a solvent method production process, the method avoids the use of a large amount of organic solvents, has environment-friendly and safe production process, consumes less time in the whole production, can effectively improve the whole production efficiency of the process, and can realize the high yield of the waterborne polyurethane environment-friendly resin.
Description
Technical Field
The invention belongs to the technical field of production of waterborne polyurethane environment-friendly resin, and particularly relates to a production method of high-yield waterborne polyurethane environment-friendly resin.
Background
Polyurethane is short for polyurethane, and a high molecular compound containing repeated carbamate groups in a molecular structure is called polyurethane, and the polyurethane is the structure of [ -CO-NH-R-NH-CO-O-R-O- ] n, and is usually polymerized by a binary or multi-element organic isocyanate active hydrogen compound through a step-by-step polymerization reaction. In addition to urethane groups, urea, biuret, and the like groups are formed, so polyurethane is an adduct of isocyanate in a broad sense. The aqueous polyurethane is a polyurethane system formed by dissolving or dispersing polyurethane in water, and some aqueous polyurethanes are also called aqueous polyurethanes or water-based polyurethanes.
With the increasing maturity of the application technology of the water-based resin, a road is paved for the continuous development of the synthetic leather industry, the popularization and application of the water-based finishing agent are inevitable trends of the synthetic leather development, according to statistics, the share of the solvent-based resin which can be replaced by the water-based resin auxiliary agent is about 50 ten thousand tons per year, so the market development space is huge, the water-based resin is a polymer, and the application premise of the water-based resin is that a good production method of high-yield water-based polyurethane is required.
Disclosure of Invention
The invention aims to provide a production method of high-yield waterborne polyurethane environment-friendly resin, and aims to solve the problems that the background technology is mature day by day, a road is paved for the continuous development of the synthetic leather industry, and the popularization and application of a waterborne coating agent are inevitable trends in the development of synthetic leather, and according to statistics, the current waterborne resin auxiliary agent can replace solvent-type resin in an amount of about 50 ten thousand tons per year, so that the market development space is huge, and the waterborne resin is really a polymer, so that a good production method of high-yield waterborne polyurethane is required on the premise of application of the waterborne resin.
In order to achieve the purpose, the invention provides the following technical scheme: a production method of high-yield waterborne polyurethane environment-friendly resin comprises the following steps:
s1, taking polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI), filling the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) into a storage tank which is prepared, and applying a proper storage temperature for storage;
s2, taking out polyester polyol, cyanate ester (IPDI), Toluene Diisocyanate (TDI), and the like, sequentially adding the polyester polyol, the cyanate ester (IPDI), the Toluene Diisocyanate (TDI), and the like into a reaction kettle in proportion, and carrying out addition reaction for a period of time at a certain temperature;
s3, carrying out addition reaction on polyester polyol, IPDI and TDI to generate pre-polymerized micromolecules, and heating the pre-polymerized micromolecules again to complete the preliminary pre-polymerization reaction;
s4, adding a hydrophilic component and a chain extender into the reaction liquid in the reaction kettle;
s5, increasing the temperature in the reaction kettle, and performing chain extension reaction for a period of time at a certain temperature to form a chain-shaped macromolecular prepolymer with hydrophilic groups to complete the chain extension reaction;
s6, adding a small amount of environment-friendly diluent into the prepolymer after the chain extension reaction for dilution, adding dimethylethanolamine to neutralize carboxyl into ammonium carboxylate groups, and performing neutralization reaction;
s7, automatically discharging the neutralized semi-finished product raw material into a dispersion kettle through a discharge hole below the reaction kettle;
s8, stirring the neutralized prepolymer at a high speed for a certain time because the neutralized prepolymer is a high-viscosity viscous liquid due to the acting force among ions;
s9, taking raw water, performing multi-stage filtration through a filter device, intercepting suspended matters and colloidal impurities in the water, reducing the turbidity of reverse osmosis inlet water, and then removing most of soluble salts, colloids, organic matters and microorganisms in the water through a high-pressure pump in combination with a reverse osmosis membrane to obtain pure water;
s10, adding the pure water obtained in the step S9 and an emulsifying agent into the reaction liquid in the high-speed stirring process, and dispersing the pure water and the emulsifying agent into water under the action of strong shearing force to ensure that the reaction liquid slowly becomes stable aqueous polyurethane resin;
and S11, discharging the produced waterborne polyurethane resin through a discharge hole below the dispersion kettle, and canning.
Preferably, in the S1, the preservation temperature of the filled polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI) is 30 ℃ to 40 ℃.
Preferably, in S2, the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) are added in a ratio of 7.5:1.6:1.1, 150 parts, 31 parts and 23 parts are respectively added, the reaction temperature is 70 ℃, and the reaction time is 3 hours.
Preferably, in the step S3, the temperature for reheating the pre-polymerized small molecules is 70-110 ℃.
Preferably, in S4, the hydrophilic component is dimethylolpropionic acid or trimethylolpropane, the chain extender is ethylenediamine, the addition amounts of dimethylolpropionic acid or trimethylolpropane are 15 parts and 16 parts, and the addition amount of ethylenediamine is 10 parts.
Preferably, in the S5, the temperature is 75-85 ℃, and the reaction time is 1 h.
Preferably, in S6, the environmentally friendly diluent is acetone and N-methylpyrrolidone, and the addition amount is 6 parts and 6 parts.
Preferably, in the step S8, the stirring time is 55min-65 min.
Preferably, in S10, the emulsifier is a mixed solution of ethylene glycol butyl ether, methyl acrylate and butyl acrylate.
Compared with the prior art, the invention has the beneficial effects that: the production process has the characteristics of simple process and low cost, compared with the solvent method production process, the method avoids the use of a large amount of organic solvents, is environment-friendly and safe in production process, consumes less time in integral production, can effectively improve the integral efficiency of the process production, and can realize the high yield of the waterborne polyurethane environment-friendly resin. The water resistance, the solvent resistance and the hardness are not influenced under the conditions that the high temperature resistance reaches 170 ℃, the low temperature resistance reaches-50 ℃, the low temperature flexing resistance reaches below-20 ℃ per 25 ten thousand times and the wear resistance reaches above 8 ten thousand times.
The important details in the present invention are as follows:
polyester polyol: organic materials, typically those prepared by the condensation (or transesterification) of organic dicarboxylic acids (anhydrides or esters) with polyhydric alcohols (including diols) or by the polymerization of lactones with polyhydric alcohols. The dibasic acid may be phthalic acid, phthalic anhydride or its ester, adipic acid, halogenated phthalic acid, etc. The polyhydric alcohol may be ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, etc. Because polyester polyols of different varieties have different types or different preparation processes and different properties, several important indexes for the polyester polyols are hydroxyl value, acid value, moisture, viscosity, molecular weight, density, chroma and the like. Characteristics and uses of polyester polyols: the polyester polyurethane contains more ester groups, amino groups and other polar groups in molecules, so that the polyester polyurethane has strong cohesive strength and adhesive force, high strength and wear resistance, and the molecular weight of polyester polyol adopted in the project is 2000-4000.
Cyanate ester: IPDI for short; a colorless to yellowish liquid; molecular formula C12H18N2O 2; molecular weight: 222.29; relative density (water ═ 1): 1.0615, respectively; melting point: -60 ℃; boiling point: 158 ℃ (15 mmHg); flash point: 110 ℃ is adopted; water solubility: <0.1g/100mL at25 ℃; the open fire is combustible; the high heat energy releases toxic nitrogen oxide steam; toxic vapors may be evolved during polymerization. Is a curing agent for the hydroxyl prepolymer (i.e., polypropylene glycol) required for the polyurethane binder of the composite propellant. The preparation method is widely applied to the industries of plastics, adhesives, medicines, spices and the like, and is mainly used for preparing non-yellowing polyurethane coatings and elastomers.
Toluene diisocyanate: TDI for short, molecular formula C9H6N2O 2; molecular weight: 174.16, colorless liquid. Melting point is 19.5-21.5 ℃; boiling point 251 deg.C, 126 deg.C (1.47kPa), relative density 1.2244 (20/4 deg.C), flash point 132 deg.C. Can be mixed with ether, acetone, carbon tetrachloride, benzene, chlorobenzene and gasoline, and can be reacted with water and alcohol for decomposition. The polyurethane coating is mainly used for polyurethane products, including foamed plastics, polyurethane coatings and polyurethane rubber; polyimide fibers and adhesives have also found some applications.
Ethylene diamine: is colorless transparent viscous liquid with ammonia odor, and has molecular formula of C2H8N 2; molecular weight: 60.1. Melting point 8.5 ℃; boiling point 118 deg.C, density 0.899g/mL at25 deg.C (lit), flash point 93 deg.C (33.9 deg.C). It is soluble in water and ethanol, slightly soluble in diethyl ether, and insoluble in benzene, and has corrosive, toxic, and irritant effects, and can strongly irritate eyes, skin and respiratory organs to cause anaphylaxis. Inhalation of high concentrations of vapor can lead to death. Flammability: the oxidant is inflammable when exposed fire and high temperature occur; the combustion produces toxic nitrogen oxide fumes. It can be used in medicine, pesticide, dye, plastic, rubber, etc.
Dimethylolpropionic acid: white powder, molecular formula C5H10O 4; molecular weight 134.13; the melting point (DEG C) is more than or equal to 180; it is soluble in DMF and methanol, and insoluble in benzene and toluene. DMPA is a versatile organic feedstock. The product is a chain extender in the preparation of waterborne polyurethane, can enable the polyurethane to obtain self-emulsifying property, and can prepare self-emulsifying waterborne polyurethane with excellent stability; also can be used for preparing polyurethane aqueous emulsion type leather finishing agent, which is an upgraded and updated product of the traditional aqueous emulsion type polyacrylate leather finishing agent
Trimethylolpropane: white flaky crystal of molecular formula C6H14O 3; molecular weight: 134.17. the melting point is 56-58 ℃, the boiling point is 159-161 ℃, the flash point is 172 ℃, the solvent is easy to dissolve in water, ethanol, propanol, glycerol and dimethylformamide and is difficult to dissolve in aliphatic hydrocarbon and aromatic hydrocarbon. Flammability: is inflammable; the combustion produces the stimulation smog. Is a polar aprotic solvent. Has the advantages of low toxicity, high boiling point, excellent dissolving power, strong selectivity and good stability.
N-methylpyrrolidone: the appearance is colorless to light yellow transparent liquid, and the molecular formula is C5H9 NO; molecular weight: 99.13. melting point-24 deg.C, boiling point 204 deg.C, and flash point 91 deg.C, and can be dissolved with water, alcohol, ether, ester, ketone, halogenated hydrocarbon and aromatic hydrocarbon. Flammability: the fuel can be burnt by strong oxidant at open fire and high temperature; and toxic nitrogen oxide gas is decomposed by heating. Is a polar aprotic solvent. Has the advantages of low toxicity, high boiling point, excellent dissolving power, strong selectivity and good stability.
Calculating the capacity of the waterborne polyurethane environment-friendly resin: according to the process flow, the production process of the waterborne polyurethane and the duration of each batch are about 8 hours (including early preparation and later finishing). 1 batch is produced every day, 8 sets of production facilities are arranged in the project, 3 sets of 1000L reaction kettles and 3000L dispersion kettle facilities are arranged, the yield of each set is 1.4 t/batch, 2 sets of 2000L reaction kettles and 4000L dispersion kettle facilities are arranged, the yield of each set is 2.8 t/batch, 2 sets of 3000L reaction kettles and 7000L dispersion kettle facilities are arranged, the yield of each set is 4.2 t/batch, 1 set of 5000L reaction kettles and 10000L dispersion kettle facilities are arranged, the yield of each set is 7 t/batch, one batch is produced every day, the production time per year is 320 days, the production time per year can produce 8064t/a of the waterborne polyurethane, and can meet the production capacity requirement of 8000 t/a.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Example 1
The invention provides a technical scheme that: a production method of high-yield waterborne polyurethane environment-friendly resin comprises the following steps:
s1, taking polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI), filling the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) into a prepared storage tank, and preserving at the temperature of 30-40 ℃;
s2, taking out polyester polyol, cyanate ester (IPDI), Toluene Diisocyanate (TDI), and the like, sequentially adding the polyester polyol, the cyanate ester (IPDI), the Toluene Diisocyanate (TDI), and the like into a reaction kettle according to a proportion, and carrying out addition reaction for 3 hours at 70 ℃;
carrying out addition reaction on S3, polyester polyol, IPDI and TDI to generate pre-polymerized micromolecules, and heating the pre-polymerized micromolecules to 70-110 ℃ to complete preliminary pre-polymerization reaction;
s4, adding a hydrophilic component and a chain extender into the reaction liquid in the reaction kettle;
s5, increasing the temperature in the reaction kettle, and performing chain extension reaction for 1h at the temperature of 75-85 ℃ to form a chain-shaped macromolecular prepolymer with hydrophilic groups to complete the chain extension reaction;
s6, adding a small amount of environment-friendly diluent into the prepolymer after the chain extension reaction for dilution, adding dimethylethanolamine to neutralize carboxyl into ammonium carboxylate groups, and performing neutralization reaction;
s7, automatically discharging the neutralized semi-finished product raw material into a dispersion kettle through a discharge hole below the reaction kettle;
s8, stirring the neutralized prepolymer at a high speed for 55-65 min because the neutralized prepolymer is a high-viscosity viscous liquid due to the acting force among ions;
s9, taking raw water, performing multi-stage filtration through a filter device, intercepting suspended matters and colloidal impurities in the water, reducing the turbidity of reverse osmosis inlet water, and then removing most of soluble salts, colloids, organic matters and microorganisms in the water through a high-pressure pump in combination with a reverse osmosis membrane to obtain pure water;
s10, adding the pure water obtained in the step S9 and an emulsifying agent into the reaction liquid in the high-speed stirring process, and dispersing the pure water and the emulsifying agent into water under the action of strong shearing force to ensure that the reaction liquid slowly becomes stable aqueous polyurethane resin;
and S11, discharging the produced waterborne polyurethane resin through a discharge hole below the dispersion kettle, and canning.
The embodiment needs to be explained as follows: the following table is the daily productivity of the waterborne polyurethane environment-friendly resin:
example 2
The invention provides a technical scheme that: a production method of high-yield waterborne polyurethane environment-friendly resin comprises the following steps:
s1, taking polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI), filling the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) into a prepared storage tank, and preserving at the temperature of 30-40 ℃;
s2, taking out polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI) in a ratio of 7.5:1.6:1.1, sequentially adding 150 parts, 31 parts and 23 parts into a reaction kettle, and carrying out addition reaction for 3 hours at 70 ℃;
s3, carrying out addition reaction on polyester polyol, IPDI and TDI to generate pre-polymerized micromolecules, and heating the pre-polymerized micromolecules to 85 ℃ to complete the preliminary pre-polymerization reaction;
s4, adding a hydrophilic component and a chain extender into the reaction liquid in the reaction kettle;
s5, increasing the temperature in the reaction kettle, and performing chain extension reaction for 1h at the temperature of 80 ℃ to form a chain-shaped macromolecular prepolymer with hydrophilic groups to complete the chain extension reaction;
s6, adding a small amount of environment-friendly diluent into the prepolymer after the chain extension reaction for dilution, adding dimethylethanolamine to neutralize carboxyl into ammonium carboxylate groups, and performing neutralization reaction;
s7, automatically discharging the neutralized semi-finished product raw material into a dispersion kettle through a discharge hole below the reaction kettle;
s8, stirring the neutralized prepolymer at a high speed for 60min because the neutralized prepolymer is a high-viscosity viscous liquid due to the acting force among ions;
s9, taking raw water, performing multi-stage filtration through a filter device, intercepting suspended matters and colloidal impurities in the water, reducing the turbidity of reverse osmosis inlet water, and then removing most of soluble salts, colloids, organic matters and microorganisms in the water through a high-pressure pump in combination with a reverse osmosis membrane to obtain pure water;
s10, adding the pure water obtained in the step S9 and an emulsifying agent into the reaction liquid in the high-speed stirring process, and dispersing the pure water and the emulsifying agent into water under the action of strong shearing force to ensure that the reaction liquid slowly becomes stable aqueous polyurethane resin;
and S11, discharging the produced waterborne polyurethane resin through a discharge hole below the dispersion kettle, and canning.
The embodiment needs to be explained as follows: the hydrophilic chain extension and neutralization reaction formula is as follows:
example 3
The invention provides a technical scheme that: a production method of high-yield waterborne polyurethane environment-friendly resin comprises the following steps:
s1, taking polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI), filling the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) into a prepared storage tank, and preserving at the temperature of 30-40 ℃;
s2, taking out polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI) and sequentially adding 150 parts, 31 parts and 23 parts into a reaction kettle according to the proportion of 7.5:1.6:1.1, and carrying out addition reaction for 3 hours at 70 ℃;
s3, carrying out addition reaction on polyester polyol, IPDI and TDI to generate pre-polymerized micromolecules, and heating the pre-polymerized micromolecules to 90 ℃ to complete the preliminary pre-polymerization reaction;
s4, adding 15 parts, 16 parts and 10 parts of dimethylolpropionic acid, a hydrophilic component of trimethylolpropane and an ethylenediamine chain extender into the reaction solution in the reaction kettle;
s5, increasing the temperature in the reaction kettle, and performing chain extension reaction for 1h at the temperature of 85 ℃ to form a chain-shaped macromolecular prepolymer with hydrophilic groups to complete the chain extension reaction;
s6, adding a small amount of acetone and N-methyl pyrrolidone environment-friendly diluent into the prepolymer which is subjected to chain extension reaction for dilution, wherein the addition amount is 6 parts and 6 parts, and then adding 29 parts of dimethylethanolamine to neutralize carboxyl into ammonium carboxylate groups for neutralization reaction;
s7, automatically discharging the neutralized semi-finished product raw material into a dispersion kettle through a discharge hole below the reaction kettle;
s8, stirring the neutralized prepolymer at a high speed for 65min because the neutralized prepolymer is a high-viscosity viscous liquid due to the acting force among ions;
s9, taking raw water, performing multi-stage filtration through a filter device, intercepting suspended matters and colloidal impurities in the water, reducing the turbidity of reverse osmosis inlet water, and then removing most of soluble salts, colloids, organic matters and microorganisms in the water through a high-pressure pump in combination with a reverse osmosis membrane to obtain pure water;
s10, adding the pure water obtained in the step S9 into the reaction liquid in the high-speed stirring process, adding a mixed solution emulsifier of ethylene glycol butyl ether, methyl acrylate and butyl acrylate, and dispersing the mixture in water under the action of strong shearing force to enable the reaction liquid to slowly become stable waterborne polyurethane resin;
and S11, discharging the produced waterborne polyurethane resin through a discharge hole below the dispersion kettle, and canning.
The embodiment needs to be explained as follows: prepolymerization reaction: the addition reaction of excess IPDI, TDI and polyester polyol is as follows:
although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A production method of high-yield waterborne polyurethane environment-friendly resin is characterized by comprising the following steps: the process method comprises the following steps:
s1, taking polyester polyol, cyanate ester (IPDI) and Toluene Diisocyanate (TDI), filling the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) into a storage tank which is prepared, and applying a proper storage temperature for storage;
s2, taking out polyester polyol, cyanate ester (IPDI), Toluene Diisocyanate (TDI), and the like, sequentially adding the polyester polyol, the cyanate ester (IPDI), the Toluene Diisocyanate (TDI), and the like into a reaction kettle in proportion, and carrying out addition reaction for a period of time at a certain temperature;
s3, carrying out addition reaction on polyester polyol, IPDI and TDI to generate pre-polymerized micromolecules, and heating the pre-polymerized micromolecules again to complete the preliminary pre-polymerization reaction;
s4, adding a hydrophilic component and a chain extender into the reaction liquid in the reaction kettle;
s5, increasing the temperature in the reaction kettle, and performing chain extension reaction for a period of time at a certain temperature to form a chain-shaped macromolecular prepolymer with hydrophilic groups to complete the chain extension reaction;
s6, adding a small amount of environment-friendly diluent into the prepolymer after the chain extension reaction is finished for dilution, adding dimethylethanolamine to neutralize carboxyl into ammonium carboxylate groups, and performing neutralization reaction;
s7, automatically discharging the neutralized semi-finished raw materials into a dispersion kettle through a discharge hole below the reaction kettle;
s8, stirring the neutralized prepolymer at a high speed for a certain time because the neutralized prepolymer is a high-viscosity viscous liquid due to the acting force among ions;
s9, taking raw water, performing multi-stage filtration through a filter device, intercepting suspended matters and colloidal impurities in the water, reducing the turbidity of reverse osmosis inlet water, and then removing most of soluble salts, colloids, organic matters and microorganisms in the water through a high-pressure pump in combination with a reverse osmosis membrane to obtain pure water;
s10, adding the pure water obtained in the step S9 and an emulsifier into the reaction liquid in the high-speed stirring process, and dispersing the pure water and the emulsifier into water under the action of strong shearing force to ensure that the reaction liquid slowly becomes stable waterborne polyurethane resin;
and S11, discharging the produced waterborne polyurethane resin through a discharge hole below the dispersion kettle, and canning.
2. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S1, the storage temperature of the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) after filling is 30-40 ℃.
3. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S2, the polyester polyol, the cyanate ester (IPDI) and the Toluene Diisocyanate (TDI) are added in a ratio of 7.5:1.6:1.1, 150 parts, 31 parts and 23 parts are respectively added, the reaction temperature is 70 ℃, and the reaction time is 3 hours.
4. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S3, the temperature for reheating the pre-polymerized micromolecules is 70-110 ℃.
5. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S4, the hydrophilic components are dimethylolpropionic acid and trimethylolpropane, the chain extender is ethylenediamine, the addition amount of the dimethylolpropionic acid and the trimethylolpropane is 15 parts and 16 parts, and the addition amount of the ethylenediamine is 10 parts.
6. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S5, the temperature is 75-85 ℃, and the reaction time is 1 h.
7. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in S6, the environment-friendly diluent is acetone and N-methyl pyrrolidone, and the addition amount is 6 parts and 6 parts.
8. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the step S8, the stirring time is 55-65 min.
9. The method for producing a high-yield waterborne polyurethane environment-friendly resin as claimed in claim 1, wherein the method comprises the following steps: in the S10, the emulsifier is a mixed solution of ethylene glycol butyl ether, methyl acrylate and butyl acrylate.
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