CN111205432A - Polyurethane curing agent and preparation method thereof - Google Patents
Polyurethane curing agent and preparation method thereof Download PDFInfo
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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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
- C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
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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
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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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention discloses a polyurethane curing agent and a preparation method thereof, and relates to the technical field of curing agents. The technical key points are as follows: a polyurethane curing agent comprises the following components in parts by weight: terephthalic acid: 5-10 parts; low molecular weight polyol: 8-13 parts; diethylene glycol: 5-8 parts; ethyl acetate: 10-15 parts; n-butyl acetate: 10-15 parts; toluene diisocyanate: 15-20 parts of a solvent; diphenylmethane-4, 4' -diisocyanate: 15-20 parts of a solvent; catalyst: 0.5-1 part; dispersing agent: 1-3 parts of polyurethane curing agent, wherein the low molecular polyester polyol synthesized in advance is used as a prepolymer to replace trimethylolpropane, and the obtained polyurethane curing agent has excellent performance and low synthesis cost.
Description
Technical Field
The invention relates to the technical field of curing agents, in particular to a polyurethane curing agent and a preparation method thereof.
Background
The polyurethane coating is a common coating at present and can be divided into a double-component polyurethane coating and a single-component polyurethane coating; two-component polyurethane coatings are generally composed of two parts, namely an isocyanate prepolymer and a hydroxyl-containing resin, and are generally referred to as a curing agent component and a main agent component; wherein the curing agent is also known as a curing agent or a crosslinking agent. The polyurethane coating curing agent can stably coexist with resin for a long time at normal temperature, isocyanate (-NCO) groups released by the curing agent react with hydroxyl, carboxyl, amino and other groups on a resin molecular chain to form a cross-linked network during heat treatment, and the cross-linking degree of an obtained paint film is improved, so that the system has higher resistance and tolerance.
The invention discloses a synthesis method of a toluene diisocyanate-trimethylolpropane polyurethane curing agent in Chinese invention application patent with application publication number CN106589305A, wherein toluene diisocyanate and trimethylolpropane are used as main addition raw materials, other oxidants, solvents and other auxiliaries are added to synthesize the polyurethane curing agent, and the synthesis method is simple and convenient to operate. However, the price of toluene diisocyanate and trimethylolpropane is high, which results in that the synthesis cost of the polyurethane curing agent is greatly increased.
Therefore, a new solution is needed to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polyurethane curing agent which has the advantages of excellent performance and low price.
The second purpose of the invention is to provide a preparation method of the polyurethane curing agent, which has the advantages of simple synthesis method and convenient operation.
In order to achieve the first purpose, the invention provides the following technical scheme:
a polyurethane curing agent comprises the following components in parts by weight:
terephthalic acid: 5-10 parts;
low molecular weight polyol: 8-13 parts;
diethylene glycol: 5-8 parts;
ethyl acetate: 10-15 parts;
n-butyl acetate: 10-15 parts;
toluene diisocyanate: 15-20 parts of a solvent;
diphenylmethane-4, 4' -diisocyanate: 15-20 parts of a solvent;
catalyst: 0.5-1 part;
dispersing agent: 1-3 parts.
By adopting the technical scheme, the low-molecular polyester polyol with a certain branching degree is synthesized in advance to be used as a prepolymer to replace common trimethylolpropane and then is subjected to addition reaction with diisocyanate, and in addition, the diisocyanate is compounded by low-price and low-toxicity diphenylmethane-4, 4' -diisocyanate and toluene diisocyanate, so that the performance can be improved, the cost can be reduced, and the pollution can be reduced. The polyurethane curing agent prepared by the method has the advantages of similar performance of the traditional curing agent and low price.
More preferably, the low molecular weight polyol is a mixture of 1, 4-butanediol and castor oil in a weight ratio of 2: 1.
By adopting the technical scheme, the more the hydroxyl groups of the low-molecular-weight polyol are, the larger the adhesion force of the curing agent to the coating film is, but the same is the coating film with larger viscosity and poor solubility, and the 1, 4-butanediol and the castor oil are compounded for use, so that the prepared curing agent has better performance, the coating film after use has larger adhesion force and high bonding strength.
More preferably, the catalyst is a combination of dibutyltin dilaurate and dibutyltin diacetate in a weight ratio of 1: 1.
By adopting the technical scheme, the catalytic speed of the dibutyltin diacetate is higher than that of the dibutyltin dilaurate, and when the dibutyltin dilaurate and the dibutyltin diacetate are compounded for use, the acetic acid smell in a system can be reduced while the higher catalytic speed can be realized.
More preferably, the dispersant is stearic acid.
By adopting the technical scheme, the stearic acid is also named as octadecanoic acid, is safe and non-toxic, does not influence human health, can reduce the agglomeration phenomenon of the raw materials of the curing agent during reaction synthesis, and improves the compatibility among the raw materials and the solubility in a solvent.
More preferably, the polyurethane curing agent also comprises 1-3 parts by weight of antimony trioxide.
By adopting the technical scheme, the antimony trioxide has good flame retardance, and the antimony trioxide can endow a coating film with good flame retardance when added into a curing agent.
In order to achieve the second purpose, the invention provides the following technical scheme:
the preparation method of the polyurethane curing agent is characterized by comprising the following steps:
s1, putting terephthalic acid, diethylene glycol, low molecular weight polyol and a catalyst into a reaction tank according to the corresponding weight parts, introducing nitrogen for 10min, heating and stirring under the nitrogen atmosphere, controlling the temperature at 230 ℃ and 250 ℃, sampling every 0.5h to determine the acid value, cooling to 25 ℃ after the acid value is lower than 0.5mgKOH/g, and discharging to obtain a low molecular weight polyester polyol prepolymer;
s2, adding toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, ethyl acetate, n-butyl acetate and a dispersing agent into a reaction tank, stirring and heating to 50-60 ℃, then adding a low-molecular polyester polyol prepolymer, reacting for 2-3h, heating to 75 ℃, adding a catalyst, reacting for 1-2h, cooling to 25 ℃, and discharging to obtain the polyurethane curing agent.
By adopting the technical scheme and the mode, the prepolymer of the low-molecular polyester polyol is synthesized firstly, then the prepolymer is reacted and synthesized with the diisocyanate, the temperature is raised and the catalyst is added at the later stage of the reaction, so that the reaction of-NCO and hydroxyl can be effectively catalyzed, the conversion rate is improved, and the viscosity of the curing agent is further reduced. By adopting the synthesis mode, the operation is simple, less synthesis equipment is used, and the performance of the synthesized polyurethane curing agent is excellent.
More preferably, the acid ester of the low molecular polyester polyol is 0.3 to 0.5 mgKOH/g.
By adopting the technical scheme, the terminal carboxyl group reacts with isocyanate to generate amide and release carbon dioxide, so that not only is chain termination caused, but also bubbles are formed, and the residual acid in the polyester can generate adverse effect on the polyurethane reaction and reduce the hydrolytic stability of the polyurethane, so that the control of the acid ester of the low-molecular polyester polyol is low and is between 0.3 and 0.5mgKOH/g, and the viscosity of the synthesized curing agent is low.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the invention synthesizes low molecular polyester polyol with a certain branching degree in advance as prepolymer to replace common trimethylolpropane, and then carries out addition reaction with diisocyanate to synthesize polyurethane curing agent, the used raw materials are low in price, and the curing agent has excellent performance;
(2) the diisocyanate is compounded by low-price and low-toxicity diphenylmethane-4, 4' -diisocyanate and toluene diisocyanate, so that the performance can be improved, the cost can be reduced, and the pollution can be reduced;
(3) the invention also provides a polyurethane curing agent synthesis method which is simple to operate and uses less equipment, the reaction conditions are easy to control, the conversion rate is higher, and the obtained curing agent has high adhesive force and low viscosity.
Drawings
FIG. 1 is a flow chart of the process for synthesizing the polyurethane curing agent in example 1.
Detailed Description
The invention will be described in detail below with reference to fig. 1 and an embodiment.
Example 1: the polyurethane curing agent comprises the following components in parts by weight as shown in Table 1, and is prepared by the following steps:
s1, sequentially putting terephthalic acid, diethylene glycol, low molecular weight polyol and a catalyst into a reaction tank according to the corresponding weight parts in the table 1, introducing nitrogen for 10min to discharge air in the tank, heating and stirring under the nitrogen atmosphere, wherein the reaction temperature is 230 ℃, the stirring speed is 100r/min, sampling every 0.5h to measure the acid value, when the acid value is lower than 0.5mgKOH/g, measuring the acid ester of the reaction system in the embodiment to be 0.4mgKOH/g, cooling to 25 ℃, discharging to obtain a low molecular weight polyester polyol prepolymer, wherein in the embodiment, the hydroxyl value of the obtained low molecular weight polyester polyol prepolymer is 130 mgKOH/g;
s2, adding toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, ethyl acetate, n-butyl acetate and stearic acid into a reaction tank according to the corresponding weight parts in the table 1, stirring and heating to 50 ℃ at the rotating speed of 100r/min, then adding a low molecular weight polyester polyol prepolymer, reacting for 3 hours, heating to 75 ℃, then adding a catalyst, reacting for 1 hour, cooling to 25 ℃, and discharging to obtain the polyurethane curing agent, wherein the NCO content of the synthesized polyurethane curing agent is 12.13%.
Examples 2 to 6: a polyurethane curing agent is different from example 1 in that each component and the corresponding weight parts are shown in Table 1.
TABLE 1 Components and parts by weight of examples 1-6
Example 7: a polyurethane curing agent, which is different from the polyurethane curing agent in example 6 in that the step S2 is specifically configured as follows: adding toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, ethyl acetate, n-butyl acetate and stearic acid into a reaction tank, stirring and heating to 60 ℃, then adding a low-molecular polyester polyol prepolymer, reacting for 2 hours, heating to 75 ℃, adding a catalyst, reacting for 2 hours, cooling to 25 ℃, and discharging to obtain the polyurethane curing agent.
Example 8: a polyurethane curing agent was different from example 1 in that 1 part of antimony trioxide was further added at the time of adding the catalyst at step S2.
Example 9: a polyurethane curing agent was different from example 6 in that 3 parts of antimony trioxide was further added at the time of adding the catalyst in the 2-step.
Comparative example 1: a polyurethane curing agent, a toluene diisocyanate-trimethylolpropane polyurethane curing agent disclosed in the Chinese invention application patent with application publication No. CN106589305A was used as comparative example 1.
Comparative example 2: a polyurethane curing agent was different from that of example 1 in that trimethylolpropane was used instead of the low-molecular polyester polyol prepolymer obtained in the step S1.
Comparative example 3: a polyurethane curing agent was different from example 1 in that the acid value of the reaction system in the S1 step was controlled to be 1 mgKOH/g.
Comparative example 4: a polyurethane curing agent is different from the polyurethane curing agent in example 1 in that the hydroxyl value of the low molecular polyester polyol prepolymer in the step S1 is controlled to be 100mgKOH/g, and the NCO content of the polyurethane curing agent synthesized in the step S2 is 6%.
Comparative example 5: a polyurethane curing agent was different from example 1 in that 1, 4-butanediol was used in an amount of 12 parts and castor oil was used in an amount of 6 parts in the S1 step.
Performance testing
The polyurethane curing agents obtained in examples 1 to 9 and comparative examples 1 to 5 were mixed with a Bayer waterborne hydroxyacrylic resin 2470 at a molar ratio of NCO to OH of 1:1 to obtain polyurethane coatings, and the properties thereof were measured, and the results are shown in Table 2.
Hardness: the test is carried out according to GB/T6739-2006 "determination of paint film hardness by colored paint and varnish pencil method".
Curing time: and (3) coating the prepared polyurethane coating on a heating plate, keeping the temperature of the heating plate constant at 120 ℃, and observing the heating and curing time of the sample.
Adhesion force: the adhesion of the polyurethane coating was tested according to GB/T1720-1979 "paint film adhesion test".
Flexibility: testing according to GB/T1731-1993 paint film flexibility determination, upward pressing a test board paint film on a shaft rod with a specified diameter by two hands, bending the test board around the shaft rod within 2-3s by using the force of two thumbs, wherein the two thumbs are symmetrical to the central line of the shaft rod after bending, observing the paint film by using a magnifying lens after bending, checking whether the paint film generates damage phenomena such as reticulation, cracks, namely peeling and the like, and expressing the flexibility of the paint film by the diameter of the minimum shaft rod which does not cause the damage of the paint film.
Yellowing resistance index: the yellowing resistance of polyurethane coatings was tested for Δ YI according to GB/T2409-19801, test methods for yellow index of plastics.
As can be seen from the test data in Table 2, the polyurethane coatings in examples 1-9 have higher hardness, shorter curing time, higher adhesion and flexibility, and excellent yellowing resistance as well as the test data in comparative example 2, which shows that the polyurethane curing agent prepared by the invention also has paint preparation performance, and the raw materials used by the invention are wide in source, low in price, low in preparation cost, and suitable for large-scale production.
Table 2 results of performance testing
| Detecting items | Hardness/grade | Curing time/s | Adhesion/grade | Flexibility/mm | Yellowing resistance index/delta YI |
| Example 1 | 5Ⅱ | 81 | 0 | 1±0.1 | 1.01 |
| Example 2 | 5Ⅱ | 80 | 0 | 1±0.1 | 1.02 |
| Example 3 | 5Ⅱ | 83 | 0 | 1±0.1 | 1.01 |
| Example 4 | 5Ⅱ | 81 | 0 | 1±0.1 | 1.01 |
| Example 5 | 5Ⅱ | 82 | 0 | 1±0.1 | 1.01 |
| Example 6 | 5Ⅱ | 83 | 0 | 1±0.1 | 1.01 |
| Example 7 | 5Ⅱ | 81 | 0 | 1±0.1 | 1.02 |
| Example 8 | 5Ⅱ | 85 | 0 | 1±0.1 | 1.02 |
| Example 9 | 5Ⅱ | 83 | 0 | 1±0.1 | 1.01 |
| Comparative example 1 | 5Ⅱ | 83 | 1 | 1±0.1 | 1.03 |
| Comparative example 2 | 5Ⅱ | 82 | 0 | 1±0.1 | 1.02 |
| Comparative example 3 | 4Ⅱ | 96 | 2 | 2±0.1 | 1.31 |
| Comparative example 4 | 3Ⅱ | 95 | 2 | 2±0.1 | 1.28 |
| Comparative example 5 | 3Ⅱ | 105 | 2 | 2±0.1 | 1.33 |
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. The polyurethane curing agent is characterized by comprising the following components in parts by weight:
terephthalic acid: 5-10 parts;
low molecular weight polyol: 8-13 parts;
diethylene glycol: 5-8 parts;
ethyl acetate: 10-15 parts;
n-butyl acetate: 10-15 parts;
toluene diisocyanate: 15-20 parts of a solvent;
diphenylmethane-4, 4' -diisocyanate: 15-20 parts of a solvent;
catalyst: 0.5-1 part;
dispersing agent: 1-3 parts.
2. The polyurethane curing agent according to claim 1, wherein the low molecular weight polyol is a mixture of 1, 4-butanediol and castor oil in a weight ratio of 2: 1.
3. The polyurethane curing agent of claim 1, wherein the catalyst is a combination of dibutyltin dilaurate and dibutyltin diacetate in a weight ratio of 1: 1.
4. The polyurethane curing agent according to claim 1, wherein the dispersant is stearic acid.
5. The polyurethane curing agent according to claim 1, further comprising 1 to 3 parts by weight of antimony trioxide.
6. The method for preparing a polyurethane curing agent according to any one of claims 1 to 5, comprising the steps of:
s1, putting terephthalic acid, diethylene glycol, low molecular weight polyol and a catalyst into a reaction tank according to the corresponding weight parts, introducing nitrogen for 10min, heating and stirring under the nitrogen atmosphere, controlling the temperature at 230 ℃ and 250 ℃, sampling every 0.5h to determine the acid value, cooling to 25 ℃ after the acid value is lower than 0.5mgKOH/g, and discharging to obtain a low molecular weight polyester polyol prepolymer;
s2, adding toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, ethyl acetate, n-butyl acetate and a dispersing agent into a reaction tank, stirring and heating to 50-60 ℃, then adding a low-molecular polyester polyol prepolymer, reacting for 2-3h, heating to 75 ℃, adding a catalyst, reacting for 1-2h, cooling to 25 ℃, and discharging to obtain the polyurethane curing agent.
7. The production method according to claim 6, wherein the acid ester of the low molecular polyester polyol is 0.3 to 0.5 mgKOH/g.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250838A (en) * | 2020-10-13 | 2021-01-22 | 固德电材系统（苏州）股份有限公司 | Curing agent for mica adhesive glue and preparation method thereof |
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