CN115260445B - Preparation and application methods of 1, 5-pentanediisocyanate curing agent - Google Patents
Preparation and application methods of 1, 5-pentanediisocyanate curing agent Download PDFInfo
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- CN115260445B CN115260445B CN202210940305.5A CN202210940305A CN115260445B CN 115260445 B CN115260445 B CN 115260445B CN 202210940305 A CN202210940305 A CN 202210940305A CN 115260445 B CN115260445 B CN 115260445B
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation and application method of a 1, 5-pentanediisocyanate curing agent, which is characterized in that: under the protection of nitrogen, adding solvent, 1, 5-pentanediisocyanate, trimethylolpropane and catalyst, reacting at 70-75 ℃, adding terminator when the NCO value of the analysis reaction system reaches 8-9%, and evaporating the solvent to obtain viscous liquid 1, 5-pentanediisocyanate curing agent. The paint is used after being painted with hydroxy acrylic acid according to NCO/OH=1:1. The preparation method of the curing agent is simple, is convenient for industrial production, and the prepared paint film has excellent performance and good weather resistance, and is more suitable for the field with higher requirements on the quality of the paint film.
Description
Technical Field
The invention belongs to the field of polyurethane application, and particularly relates to a polyurethane curing agent and an application method thereof.
Background
Polyurethane coatings are a relatively common class of coatings and can be classified into two-component polyurethane coatings and one-component polyurethane coatings. Two-component polyurethane coatings are generally composed of two parts, an isocyanate prepolymer and a hydroxyl-containing resin, commonly referred to as a curative component and a main component. The paint has the advantages of easy drying, wear resistance, high hardness, good plumpness, good flexibility, easy polishing, strong compatibility with solvents, stable performance and the like, and is a paint variety with very promising development prospect. The main application directions are wood coating, automobile repair coating, anti-corrosion coating, floor coating, electronic coating, special coating, polyurethane waterproof coating and the like.
The curing agent component of the polyurethane coating generally comprises three components of diisocyanate biuret, trimer and adduct. The existing market is widely applied to TDI trimer, TDI adduct, HDI biuret and HDI trimer, and the curing agent prepared from the aromatic isocyanate represented by TDI has poor weather resistance and is not suitable for being applied to places with high weather resistance requirements; the aliphatic isocyanate represented by HDI has high weather resistance and is favored by customers. However, HDI has a limited raw material, so that the yield of the curing agent is low, and the requirement of mass application in the market cannot be met. The 1, 5-pentanediamine is prepared by taking 1, 5-pentanediamine prepared by a biological method as a raw material and is prepared after photochemical reaction, the raw material has wide sources and similar properties to HDI, and can be used for replacing the HDI.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and application, and provides a preparation method and an application method of a 1, 5-pentanediisocyanate curing agent.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of a 1, 5-pentanediisocyanate curing agent is characterized by comprising the following specific steps: under the protection of nitrogen, adding solvent, 1, 5-pentanediisocyanate, trimethylolpropane and catalyst into a reaction kettle, stirring uniformly at the stirring speed of 280-300 r/min, controlling the reaction temperature to 70-75 ℃, cooling to 60 ℃ when the NCO value of the analysis reaction system reaches 8-9%, adding a terminator, reacting for 0.5h under the heat preservation, cooling to room temperature to obtain a crude product of the 1, 5-pentanediisocyanate curing agent, and evaporating the solvent to obtain a viscous liquid 1, 5-pentanediisocyanate curing agent.
The solvent is butyl acetate, and the addition amount is the sum of the mass of the 1, 5-pentanediisocyanate and the mass of the trimethylolpropane.
The catalyst is tri-n-butyl phosphorus, and the addition amount is 0.3-0.5% of the mass of the 1, 5-pentanediisocyanate.
The terminator is benzoyl chloride, and the addition amount of the terminator is 60% of the mass of the catalyst.
The water content of the trimethylolpropane is less than 0.02 percent (mass fraction), and the addition amount is 8-10 percent of the mass of the 1, 5-pentanediisocyanate.
The solvent evaporating method is molecular film evaporator treatment.
The application method of the 1, 5-pentanediisocyanate curing agent comprises the following steps: the 1, 5-pentanediisocyanate curing agent and the hydroxy acrylic acid are prepared into paint according to the mol ratio of NCO/OH 1:1.
The beneficial effects of the invention are as follows: the polyurethane curing agent is directly synthesized by adopting the 1, 5-pentanediisocyanate component by a one-step method, the production cost is low, the industrial production is convenient, the prepared paint film has excellent performance, can replace HDI curing agents, has good weather resistance, and is more suitable for the field with higher requirements on the quality of the paint film.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
Under the protection of nitrogen, 847g of butyl acetate, 770g of 1, 5-pentanediisocyanate monomer, 77g of trimethylolpropane and 2.31g of tri-n-butyl phosphorus are added into a reaction kettle, stirring is started, the stirring speed is 280 r/min, after the reaction is carried out for 6 hours at 70 ℃, the NCO value of a reaction system is determined to be 8.10%, benzoyl chloride is added into the reaction system after the temperature is reduced to 60 ℃, the reaction is carried out for 0.39 g of benzoyl chloride, the reaction is carried out for 0.5 hour after the heat preservation, the reaction is cooled to room temperature, the crude product of the 1, 5-pentanediisocyanate curing agent is obtained, butyl acetate is distilled off, and the viscous liquid which is the 1, 5-pentanediisocyanate curing agent is obtained.
After the prepared 1, 5-pentanediisocyanate curing agent and hydroxy acrylic acid are prepared into paint according to NCO/OH (molar ratio) =1:1, the performance index of the paint film is measured.
The physicochemical index of the 1, 5-pentanediisocyanate curing agent is analyzed and shown in the table (I).
The performance index after the paint is matched with the hydroxy acrylic acid is shown in a table (II).
Example 2
Under the protection of nitrogen, adding 839g of butyl acetate, 770g of 1, 5-pentanediisocyanate monomer, 69g of TMP and 3.10g of tri-n-butyl phosphorus into a reaction kettle, starting stirring, stirring at a rotation speed of 290 r/min, reacting for 5h at 73 ℃, determining the NCO% value of a reaction system to be 8.99%, cooling to 60 ℃, adding 1.86g of benzoyl chloride, reacting for 0.5h at a temperature, cooling to room temperature to obtain a crude product of the 1, 5-pentanediisocyanate curing agent, and evaporating butyl acetate to obtain a viscous liquid which is the 1, 5-pentanediisocyanate curing agent.
After the prepared 1, 5-pentanediisocyanate curing agent and hydroxy acrylic acid are prepared into paint according to NCO/OH (molar ratio) =1:1, the performance index of the paint film is measured.
The physicochemical index of the 1, 5-pentanediisocyanate curing agent is analyzed and shown in the table (I).
The performance index after the paint is matched with the hydroxy acrylic acid is shown in a table (II).
Example 3
Under the protection of nitrogen, 832g of solvent butyl acetate, 770g of 1, 5-pentanediisocyanate monomer, 62g of TMP and 3.85g of tri-n-butyl phosphorus are added into a reaction kettle, stirring is started, the stirring speed is 300 r/min, after the reaction is carried out for 5.5h at 75 ℃, the NCO value of the reaction system is determined to be 8.64%, benzoyl chloride is added after the temperature is reduced to 60 ℃, 2.31g of benzoyl chloride is added, the reaction is carried out for 0.5h at a temperature maintained, the reaction kettle is cooled to room temperature, the crude product of the 1, 5-pentanediisocyanate curing agent is obtained, butyl acetate is distilled off, and the viscous liquid is the 1, 5-pentanediisocyanate curing agent.
After the prepared 1, 5-pentanediisocyanate curing agent and hydroxy acrylic acid are prepared into paint according to NCO/OH (molar ratio) =1:1, the performance index of the paint film is measured.
The physicochemical index of the 1, 5-pentanediisocyanate curing agent is analyzed and shown in the table (I).
The performance index after the paint is matched with the hydroxy acrylic acid is shown in a table (II).
Table (I) physicochemical index of 1, 5-pentanediisocyanate curing agent
| Physical and chemical index | Example 1 | Example 2 | Example 3 |
| NCO/% | 16.15 | 17.93 | 17.20 |
| Viscosity (25 ℃ C.)/P | 2000 | 1760 | 1890 |
| Residual 1, 5-pentanediisocyanate monomer/% | 0．17 | 0.21 | 0.19 |
Table (II) Performance index after paint formulation with hydroxyacrylic acid
| Performance index | Example 1 | Example 2 | Example 3 |
| Young's modulus kg/cm | 402 | 390 | 411 |
| Tensile strength kg/cm | 217 | 201 | 219 |
| Elongation at break% | 78 | 72 | 77 |
| Surface drying time/min, 23 DEG C | 180 | 200 | 189 |
| Hardness of | 2H | 2H | 2H |
| Color difference UVA,1000h | 1.7 | 1.5 | 1.6 |
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A preparation method of a 1, 5-pentanediisocyanate curing agent is characterized by comprising the following specific steps: under the protection of nitrogen, adding solvent, 1, 5-pentanediisocyanate, trimethylolpropane and catalyst into a reaction kettle, stirring uniformly at the stirring speed of 280-300 r/min, controlling the reaction temperature to 70-75 ℃, cooling to 60 ℃ when the NCO value of the analysis reaction system reaches 8-9%, adding a terminator, reacting for 0.5h under the heat preservation, cooling to room temperature to obtain a crude product of the 1, 5-pentanediisocyanate curing agent, and evaporating the solvent to obtain a viscous liquid 1, 5-pentanediisocyanate curing agent.
2. The method for preparing the 1, 5-pentanediisocyanate curing agent according to claim 1, wherein: the solvent is butyl acetate, and the addition amount is the sum of the mass of the 1, 5-pentanediisocyanate and the mass of the trimethylolpropane.
3. The method for preparing the 1, 5-pentanediisocyanate curing agent according to claim 1, wherein: the catalyst is tri-n-butyl phosphorus, and the addition amount is 0.3-0.5% of the mass of the 1, 5-pentanediisocyanate.
4. The method for preparing the 1, 5-pentanediisocyanate curing agent according to claim 1, wherein: the terminator is benzoyl chloride, and the addition amount of the terminator is 60% of the mass of the catalyst.
5. The method for preparing the 1, 5-pentanediisocyanate curing agent according to claim 1, wherein: the water content of the trimethylolpropane is less than 0.02% by mass, and the addition amount is 8-10% by mass of the 1, 5-pentanediisocyanate.
6. The method for preparing the 1, 5-pentanediisocyanate curing agent according to claim 1, wherein: the solvent evaporating method is molecular film evaporator treatment.
7. The method for using the 1, 5-pentanediisocyanate curing agent obtained by the preparation method according to any one of claims 1 to 6, wherein: the 1, 5-pentanediisocyanate curing agent and the hydroxy acrylic acid are prepared into paint according to the mol ratio of NCO/OH 1:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210940305.5A CN115260445B (en) | 2022-08-05 | 2022-08-05 | Preparation and application methods of 1, 5-pentanediisocyanate curing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210940305.5A CN115260445B (en) | 2022-08-05 | 2022-08-05 | Preparation and application methods of 1, 5-pentanediisocyanate curing agent |
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| CN115260445A CN115260445A (en) | 2022-11-01 |
| CN115260445B true CN115260445B (en) | 2023-08-29 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910674A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Curing agent with high density and strong adhesive force and preparation method of curing agent |
| CN106589305A (en) * | 2016-12-15 | 2017-04-26 | 陕西启源科技发展有限责任公司 | Synthesis method of TDI-TMP (toluene diisocyanate-trimethylolpropane) polyurethane curing agent |
| WO2018023860A1 (en) * | 2016-08-01 | 2018-02-08 | 山东一诺威新材料有限公司 | Isocyanurate polyether polyol and preparation method therefor, and preparation method for coating curing agent |
| CN107709397A (en) * | 2015-06-12 | 2018-02-16 | 三井化学株式会社 | Polyisocyantates composition, polyurethane resin, two-solution curing type urethane composition and coating material |
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2022
- 2022-08-05 CN CN202210940305.5A patent/CN115260445B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709397A (en) * | 2015-06-12 | 2018-02-16 | 三井化学株式会社 | Polyisocyantates composition, polyurethane resin, two-solution curing type urethane composition and coating material |
| CN104910674A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Curing agent with high density and strong adhesive force and preparation method of curing agent |
| WO2018023860A1 (en) * | 2016-08-01 | 2018-02-08 | 山东一诺威新材料有限公司 | Isocyanurate polyether polyol and preparation method therefor, and preparation method for coating curing agent |
| CN106589305A (en) * | 2016-12-15 | 2017-04-26 | 陕西启源科技发展有限责任公司 | Synthesis method of TDI-TMP (toluene diisocyanate-trimethylolpropane) polyurethane curing agent |
Non-Patent Citations (1)
| Title |
|---|
| 廉价、快干、低游离TDI改性聚氨酯固化剂的研制;戴红斌;陈士兴;;涂料技术与文摘(12);29-30 * |
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| CN115260445A (en) | 2022-11-01 |
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