CN113105489A - Hydroxyl carborane derivative containing ether bond, modified curing agent, and preparation method and application thereof - Google Patents

Hydroxyl carborane derivative containing ether bond, modified curing agent, and preparation method and application thereof Download PDF

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CN113105489A
CN113105489A CN202110352679.0A CN202110352679A CN113105489A CN 113105489 A CN113105489 A CN 113105489A CN 202110352679 A CN202110352679 A CN 202110352679A CN 113105489 A CN113105489 A CN 113105489A
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curing agent
carborane
ether
derivative
hydroxyl
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CN113105489B (en
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黄洪
黄金泽
司徒粤
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • 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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Abstract

The invention discloses a hydroxyl carborane derivative containing ether bonds, a modified curing agent, and a preparation method and application thereof. The structural formula of the hydroxyl carborane derivative containing ether bond is one of the following formulas, wherein R1The group being-CH2CH2‑、
Figure DDA0003002627210000011
Or
Figure DDA0003002627210000012
R3The group being-CH3、‑CH2CH2CH3、‑CH(CH3)2、‑CH2Ph. The preparation steps are as follows: the o-carborane is subjected to aldehyde group formation to prepareO-carborane B-1 containing single aldehyde group; reducing and hydroxylating the aldehyde group to prepare o-carborane B-2 containing a hydroxyl group; the hydroxyl group is then subjected to a ring-opening reaction with an epoxide to form a hydroxycarborane derivative containing an ether linkage. The derivative is dripped into an isocyanate curing agent for modification to obtain the modified curing agent. The finally obtained modified curing agent has longer storage time, and after being matched with resin for paint, the obtained paint film has the characteristics of high drying speed, strong flexibility and the like.

Description

Hydroxyl carborane derivative containing ether bond, modified curing agent, and preparation method and application thereof
Technical Field
The invention belongs to the field of solvent type double-component polyurethane curing agents, and particularly relates to a hydroxyl carborane derivative containing ether bonds, a modified curing agent, and a preparation method and application thereof.
Background
Polyurethane (PU) is a generic term for polymers having a large number of urethane (-NHCOO-) structures in the main chain, and is generally produced by reacting a polyisocyanate curing agent with a polyol resin and crosslinking the resulting product. The main chain structure of PU is generally composed of hard segments and soft segments, wherein the soft segments are mostly polyhydroxy compound resin components, and the hard segments are polyisocyanate curing agents. Generally, the mechanical property and the high temperature resistance of PU can be adjusted by changing the proportion of hard segments and soft segments in PU, but the cracking, falling off and the like of a paint film still occur in the traditional PU under the condition of higher temperature. As a hard segment component in PU, the polyisocyanate curing agent cannot be stored for a long time at normal temperature due to the relatively active NCO group, and the problems of tank expansion, yellowing, viscosity increase, NCO reduction and the like often occur, so that the hard segment component is very unfavorable for long-term storage.
Carborane is a compound formed by substituting one or more boron vertices of a polyhedral boron cluster compound with carbon atoms. A large number of carborane clusters are formed due to the substitution of different numbers and positions of boron atoms by carbon atoms. Among the series of carboranes, caged-dicarbadodecaborane (C)2B10H12) Is most concerned because of its structural stability. The cage-o-carborane has the characteristic of high-temperature atomic rearrangement, can be converted into the cage-m-carborane at the temperature of 450-plus-minus-plus-minus carborane at the temperature of 650-plus-minus-plus-minus, and the conversion process.
The ether bond cohesive energy is lower and the PU material is easy to rotate, so that the ether group is inserted into the PU, the flexibility and hydrolysis resistance of a paint film can be enhanced, the system viscosity is reduced, the application range of the PU material is greatly expanded, but the mechanical property of the PU material is not as good as that of the PU material doped with polar groups such as ester groups, amino groups and the like.
At present, a plurality of methods for improving the performance of polyurethane by adopting a carborane structure or an ether bond structure emutexist, and patent CN 105860004B discloses a preparation method of carborane modified fluorine-containing polyurethane. The patent CN 111500244A discloses a carborane-containing high and low temperature resistant adhesive resin and a preparation method thereof, wherein dihydroxy carborane, hydroxyl-terminated siloxane and aromatic diacid chloride are used as raw materials to prepare diol A, and the diol A is mixed with polyisocyanate B and inorganic particles modified by a coupling agent as fillers in proportion to prepare a two-component polyurethane adhesive, which has good high and low temperature bonding strength. Patent CN 109337032a provides a method for modifying polyurethane curing agent with polyether-ether-ketone oligomer, which comprises first synthesizing a polyether-ether-ketone oligomer, and then polymerizing toluene diisocyanate to obtain the modified curing agent, thereby effectively improving the properties of hardness, flexibility, high temperature resistance, acid and alkali resistance, etc. Patent CN 201410657824.6 provides a preparation method of polyether modified HMDI waterborne polyurethane curing agent, which is to drop dehydrated polyethylene glycol monobutyl ether into H6MDI or H12And when the desired NCO content is reached in MDI, cooling and discharging to prepare the polyether modified waterborne polyurethane curing agent, wherein the polyether modified waterborne polyurethane curing agent has the characteristics of high hardness, high transparency, good scratch of a paint film, good leveling property, high fullness, good compatibility and the like with the polyurethane paint prepared from the waterborne hydroxyl component. The introduction of the carborane structure can obviously improve the performances of high and low temperature resistance, flexibility, bonding strength and the like of the polyurethane material, but the preparation viscosity is higher and the reaction is difficult to control because the o-carborane has two active hydrogen atoms; the study on carborane polyarylate is more, and how to introduce the carborane structure into the structure of an isocyanate curing agentAnd the application is limited.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly synthesizes a hydroxyl modifier containing cage-type o-carborane and ether bonds, and the hydroxyl modifier reacts with-NCO groups on an isocyanate curing agent to carry out grafting modification, so as to obtain the curing agent with longer storage time. After the modified isocyanate curing agent is matched with resin for use, a high-temperature-resistant paint film with good flexibility, high drying speed and excellent mechanical property can be obtained.
The carborane has stronger influence on the performances such as flexibility, adhesive force and the like of a coating film after being matched with resin due to larger steric hindrance, and the introduction of ether bond can just improve the situation. Therefore, the introduction of carborane and ether bond structures into the isocyanate curing agent is of great significance for prolonging the storage time of the curing agent and improving the performance of a coating film.
The hydroxyl carborane derivative containing ether bonds is synthesized to be used as a modifier to modify an isocyanate curing agent, and the ether bonds are inserted, so that the drying rate, the flexibility and other properties after film forming are improved; by inserting the o-carborane, the thermal stability of the isocyanate curing agent and the mechanical property after film forming are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydroxy carborane derivative containing an ether bond, having the formula:
Figure BDA0003002627200000031
wherein R is1The group being-CH2CH2-、
Figure BDA0003002627200000032
Figure BDA0003002627200000033
R3The group being-CH3、-CH2CH2CH3、-CH(CH3)2、-CH2Ph。
The preparation method of the hydroxyl carborane derivative containing ether bonds comprises the following steps:
(1) under the condition of inert gas atmosphere at-60 to-20 ℃, dropwise adding a hexane solution of n-butyllithium into an ether solution of o-carborane, and stirring for 10-30 min; adding an ether solution of formate into the system, raising the temperature to 0-50 ℃, and continuing to stir for 4-24 h, or adding an ether solution of a halogenated dioxolane compound into the system, raising the temperature to 0-50 ℃, continuing to stir for 4-24 h, and then adding methyl p-toluenesulfonate and continuing to stir for 1-4 h; adding a quenching agent to carry out quenching reaction, extracting the water phase by using ether, collecting the organic phase, and carrying out rotary evaporation on the organic phase to remove the residual solvent to obtain o-carborane B-1 containing a single aldehyde group;
(2) dissolving B-1 in a methanol solution, adding a reducing agent at the temperature of-10 ℃, stirring for reaction for 2-8 h, filtering and discharging, and performing rotary evaporation on a product to obtain o-carborane B-2 containing monohydroxy groups;
(3) under the alkaline condition, B-2 and epoxide react under stirring at 40-80 ℃ to obtain the hydroxyl carborane derivative containing ether bond.
Preferably, the molar ratio of n-butyllithium to o-carborane in the step (1) is 1-1.3: 1.
Preferably, the halogenated dioxolane compound in the step (1) is one or more of 2- (2-bromoethyl) -1, 3-dioxolane, 2-bromobenzaldehyde vinylaldehyde, 2- (2-bromo-5-methoxyphenyl) - [1,3] dioxolane, and 2- (2-bromophenoxymethyl) - [1,3] dioxolane.
Preferably, the formate in step (1) is methyl formate.
Preferably, the ether in step (1) is one or more of diethyl ether, propyl ether or dibutyl ether;
preferably, the quenching agent in the step (1) is one or more of dilute acetic acid solution and dilute hydrochloric acid solution;
preferably, the reducing agent in step (2) is one or more of hydrogen, sodium borohydride, lithium aluminum hydride and diborane.
Preferably, the epoxide in step (3) is one or more of propylene oxide, propyl ethylene oxide, 2-isobutyl ethylene oxide and 2-benzyl ethylene oxide.
Preferably, the alkaline environment in step (3) is an ethylenediamine solution.
A preparation method of hydroxyl carborane derivative modified curing agent containing ether bond comprises the following steps:
and (2) dropwise adding the hydroxyl carborane derivative containing ether bonds into an isocyanate curing agent at 40-80 ℃, keeping the temperature, continuously stirring and reacting for 40-60 min, cooling and discharging to obtain the hydroxyl carborane derivative containing ether bonds modified curing agent.
Preferably, the isocyanate curing agent comprises a TDI-TMP adduct, a TDI trimer curing agent or a HDI trimer curing agent.
The hydroxyl carborane derivative modified curing agent containing ether bonds prepared by the preparation method. The finally obtained modified curing agent has longer storage time and lower viscosity, and after being matched with resin for paint, the obtained paint film has the characteristics of high temperature resistance, high drying speed, strong flexibility and the like.
The application of the hydroxyl carborane derivative modified curing agent containing ether bonds in improving the performance of a paint film.
The synthetic route of the hydroxyl carborane derivative containing ether bond is as follows:
firstly, substituting active H atoms of C-H groups on cage-type o-carborane with Li atoms of n-butyllithium with one time of molar weight to obtain mono-lithiated carborane with stronger activity;
Figure BDA0003002627200000051
adding a specific electrophilic reagent into the mono-lithiated carborane for hydroformylation to obtain carborane B-1 containing a single aldehyde group;
if the electrophile is methyl formate, the reaction scheme is as follows:
Figure BDA0003002627200000052
if the electrophile is a halogenated dioxolane, the reaction formula is as follows:
Figure BDA0003002627200000061
and mixing the B-1 and a reducing agent, and reacting to obtain the o-carborane B-2 containing monohydroxy groups.
Figure BDA0003002627200000062
And B-2 and epoxide are stirred and reacted at 40-80 ℃ under the alkaline condition to obtain a final product: a hydroxyl carborane derivative modifier containing ether bond.
Figure BDA0003002627200000063
Wherein R is1The group being-CH2CH2-、
Figure BDA0003002627200000064
Figure BDA0003002627200000065
Wherein R is2The radical is
Figure BDA0003002627200000066
Wherein R is3The group being-CH3、-CH2CH2CH3、-CH(CH3)2、-CH2Ph。
The hydroxyl carborane derivative containing ether bonds is synthesized to modify the isocyanate curing agent, so that the storage time of the isocyanate curing agent is prolonged, and an obtained paint film has the characteristics of high temperature resistance, high drying speed, strong flexibility and the like after the isocyanate curing agent is matched with resin. The final structure is shown below:
Figure BDA0003002627200000071
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the hydroxyl carborane derivative containing ether bonds, prepared by the invention, modifies the isocyanate curing agent, so that the performance of the isocyanate curing agent can be obviously improved;
(2) according to the invention, the ether group and the o-carborane are introduced into the isocyanate curing agent for modification, so that the storage time of the isocyanate curing agent is prolonged, and after the isocyanate curing agent is matched with resin for paint, the obtained paint film has the characteristics of high drying speed, strong flexibility and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the following examples are only a part of the present invention and do not represent all the examples.
Example 1
Preparation of hydroxy carborane derivatives containing ether linkages:
an ether solution of o-carborane (28g) was charged to a 2L reactor under argon atmosphere and the system was cooled to-40 ℃. Subsequently, a hexane solution of n-butyllithium (13g) was gradually added dropwise to the system, and the mixture was stirred at-40 ℃ for 20 min. The dried methyl formate (6mL) was added to the system, the temperature of the system was raised to 25 ℃ and stirring was continued for 12 h. The reaction was quenched by addition of 300mL of dilute HCl solution and stirring was continued for 30 min. The mixture was taken out, the organic phase was extracted with ether, and then the extracted organic phase was subjected to rotary evaporator to remove residual moisture and ether components, to obtain 26g of the o-carborane B-1 containing a monoaldehyde group.
Dissolving 26g B-1 in a methanol solution, cooling the system to 0 ℃, then adding sodium borohydride powder into the system, stirring and reacting for 4 hours, taking out the mixture after the reduction reaction is finished, and performing rotary evaporation to obtain 24g of o-carborane B-2 containing monohydroxy. 24g B-2 was dissolved in an ethylenediamine solution, the temperature of the system was raised to 60 ℃, and then a slight excess of propylene oxide was added to the system, and the reaction was stirred under reflux for 2 hours. And (3) cooling, discharging, and carrying out rotary evaporation to obtain 34g of a final product, namely X-1.
Preparation of hydroxyl carborane derivative modified curing agent containing ether bond:
and gradually dropwise adding 34g X-1 into 1kgTDI tripolymer curing agent preheated to 60 ℃, stirring for reaction for 1h, cooling and discharging to obtain a sample named as sample 1.
Example 2
Preparation of hydroxy carborane derivatives containing ether linkages:
an ether solution of o-carborane (28g) was charged to a 2L reactor under argon atmosphere and the system was cooled to-40 ℃. Subsequently, a hexane solution of n-butyllithium (13g) was gradually added dropwise to the system, and the mixture was stirred at-40 ℃ for 20 min. The dried methyl formate (6g) was added to the system, the temperature of the system was raised to 25 ℃ and stirring was continued for 12 h. The reaction was quenched by addition of 300mL of dilute HCl solution and stirring was continued for 30 min. The mixture was taken out, the organic phase was extracted with ether, and then the extracted organic phase was subjected to rotary evaporator to remove residual moisture and ether components, to obtain 26g of the o-carborane B-1 containing a monoaldehyde group.
Dissolving 26g B-1 in a methanol solution, cooling the system to 0 ℃, then adding sodium borohydride powder into the system, stirring and reacting for 4 hours, taking out the mixture after the reduction reaction is finished, and performing rotary evaporation to obtain 24g of o-carborane B-2 containing monohydroxy. 24g B-2 was dissolved in the ethylenediamine solution, the temperature of the system was raised to 60 ℃, and then a slight excess of 2-benzyloxirane was added to the system, and the reaction was stirred under reflux for 2 hours. And (3) cooling, discharging, and carrying out rotary evaporation to obtain 38g of a final product, namely X-2.
Preparation of hydroxyl carborane derivative modified curing agent containing ether bond:
and gradually dripping 38g X-2 into 1kg of TDI trimer curing agent preheated to 60 ℃, stirring for reaction for 1h, cooling and discharging to obtain a sample named as sample 2.
Example 3
Preparation of hydroxy carborane derivatives containing ether linkages:
an ether solution of o-carborane (28g) was charged to a 2L reactor under argon atmosphere and the system was cooled to-40 ℃. Subsequently, a hexane solution of n-butyllithium (13g) was gradually added dropwise to the system, and the mixture was stirred at-40 ℃ for 20 min. Adding the dried 2- (2-bromoethyl) -1, 3-dioxolane (18g) into a system, raising the temperature of the system to 25 ℃, continuing to stir for 12h, adding 2g of p-toluenesulfonic acid into an organic phase, and continuing to stir for reaction for 1 h. The reaction was quenched by addition of 300mL of saturated ammonium chloride solution and stirring was continued for 30 min. The mixture was taken out, the organic phase was extracted with ether, and then the product after the hydroformylation reaction was subjected to a rotary evaporator to remove residual moisture and ether components, to obtain 36g of the o-carborane B-1 containing a single aldehyde group.
Dissolving 36g B-1 in a methanol solution, cooling the system to 0 ℃, then adding sodium borohydride powder into the system, stirring and reacting for 4 hours, taking out the mixture after the reduction reaction is finished, and performing rotary evaporation to obtain 34g of o-carborane B-2 containing monohydroxy. 34g B-2 was dissolved in the ethylenediamine solution, the temperature of the system was raised to 60 ℃, then a slight excess of propylene oxide was added to the system, and the reaction was stirred under reflux for 2 hours. And (4) cooling, discharging, and carrying out rotary evaporation to obtain 42g of a final product, namely X-3.
Preparation of hydroxyl carborane derivative modified curing agent containing ether bond:
and gradually dripping 42g X-3 into 1kg of TDI tripolymer curing agent preheated to 60 ℃, stirring for reaction for 1h, cooling and discharging to obtain a sample named as sample 3.
Example 4
Preparation of hydroxy carborane derivatives containing ether linkages:
an ether solution of o-carborane (28g) was charged to a 2L reactor under argon atmosphere and the system was cooled to-40 ℃. Subsequently, a hexane solution of n-butyllithium (13g) was gradually added dropwise to the system, and the mixture was stirred at-40 ℃ for 20 min. Adding the dried 2- (2-bromophenoxymethyl) - [1,3] dioxolane (26g) into the system, raising the temperature of the system to 25 ℃, continuing to stir for 12h, adding 2g of p-toluenesulfonic acid into the organic phase, and continuing to stir for reaction for 1 h. The reaction was quenched by addition of 300mL of saturated ammonium chloride solution and stirring was continued for 30 min. The mixture was taken out, the organic phase was extracted with ether, and then the product after the hydroformylation reaction was subjected to a rotary evaporator to remove residual moisture and ether components, to obtain 44g of the o-carborane B-1 containing a single aldehyde group.
Dissolving 44g B-1 in a methanol solution, cooling the system to 0 ℃, then adding sodium borohydride powder into the system, stirring and reacting for 4 hours, taking out the mixture after the reduction reaction is finished, and performing rotary evaporation to obtain 41g of o-carborane B-2 containing monohydroxy. 41g B-2 was dissolved in the ethylenediamine solution, the temperature of the system was raised to 60 ℃, and then a slight excess of propylene oxide was added to the system, and the reaction was stirred under reflux for 2 hours. And (4) cooling, discharging, and carrying out rotary evaporation to obtain 49g of a final product, namely X-4.
Preparation of hydroxyl carborane derivative modified curing agent containing ether bond:
and gradually dropwise adding 49g X-4 into 1kg of TDI trimer curing agent preheated to 60 ℃, stirring for reaction for 1h, cooling and discharging to obtain a sample named as sample 4.
Example 5
Gradually dripping the final product X-136 g in the example 1 into 1kg of TDI-TMP adduct curing agent preheated to 60 ℃, stirring for reaction for 1h, cooling and discharging to obtain a sample named as sample 5.
Example 6
Gradually dropwise adding the final product X-136 g in the example 1 into 1kg of HDI trimer curing agent preheated to 60 ℃, stirring for reaction for 1h, and cooling and discharging to obtain a sample named as sample 6.
And (3) testing thermal stability:
240g of samples 1-6, the TDI trimer curing agent A before modification, the TDI-TMP curing agent B before modification and the HDI trimer curing agent C before modification are respectively put into a 0.3L bare round bottom jar and then sealed, and then the samples are placed in an explosion-proof oven under the environment condition of 50 ℃ for storage for 15 days (equivalent to 6 months under the normal temperature environment). Finally, samples were taken and the post heat-storage viscosities of the four samples were determined as shown in table 1.
The viscosity test adopts a digital display rotary viscometer to test at 25 ℃.
Table 150 ℃/15d storage stability test results
Figure BDA0003002627200000111
As can be seen from the data in Table 1, the isocyanate curing agent modified by self-synthesizing the hydroxyl carborane derivative containing ether bond has better heat storage stability and prolongs the storage time of the isocyanate curing agent.
Testing the performance of the coating spray plate:
samples 1-4 and the TDI trimer curing agent A before modification are respectively mixed with hydroxy resin according to the proportion of NCO: OH being 1:1, the viscosity of the mixture is adjusted to 12s (coating 4-cup, 25 ℃) by using a diluent, the mixture is uniformly sprayed on a wood board containing a primer by adopting a cross spraying method, and the wood board is kept still for 48h under the constant temperature condition (25 ℃), and the film coating performance is tested.
Sample 5 and the curing agent B of the TDI-TMP adduct before modification were mixed with the hydroxy resin at a ratio of NCO: OH 1:1, respectively, the viscosity of the mixture was adjusted to 20s with a diluent (4-cup coating, 25 ℃ C.), the mixture was uniformly sprayed on a wood board containing a primer by a cross spray method, and the coating performance was tested by leaving the mixture to stand at a constant temperature (25 ℃ C.) for 48 hours.
Sample 6 and HDI trimer curing agent C before modification were mixed with hydroxy resin at a ratio of NCO: OH 1:1, respectively, the viscosity of the mixture was adjusted to 12s with a diluent (4-cup coating, 25 ℃ C.), the mixture was uniformly sprayed on a wood board containing a primer by a cross spray method, and the coating properties were tested by leaving to stand at a constant temperature (25 ℃ C.) for 48 hours.
In the test, the construction viscosity is tested according to GB/T1723-.
TABLE 2 test of the performance of the paint film after the paint preparation of samples 1-4, commercially available isocyanate curing agent and resin
Figure BDA0003002627200000121
Figure BDA0003002627200000131
As can be seen from the data in Table 2, the drying speed, pencil hardness and adhesion of the coating film prepared by the isocyanate curing agent modified by self-synthesis of the hydroxyl carborane derivative containing ether bond are all better than those of the coating film prepared by the conventional isocyanate curing agent, and the following can be obtained: an o-carborane structure is introduced into the isocyanate curing agent, so that the mechanical property of the isocyanate curing agent after paint matching and film coating can be effectively improved.
As can be seen from the data in Table 2, the flexibility of the coating film after the isocyanate curing agent modified by self-synthesized ether bond-containing hydroxyl carborane derivative is matched with paint passes through 1mm, and is also obviously better than the coating film after the conventional isocyanate curing agent is matched with paint, and the following results can be obtained: an ether bond structure is introduced into the isocyanate curing agent, so that the flexibility of the isocyanate curing agent after paint preparation and film coating can be effectively improved.
The above embodiments are only some embodiments of the present invention, and the flow description is more detailed, but not limiting the scope of the invention, and other equivalent changes and simplified substitutions made without departing from the spirit and the spirit of the invention are within the scope of the invention.

Claims (10)

1. A hydroxycarborane derivative containing an ether bond, characterized in that it has the formula:
Figure FDA0003002627190000011
wherein R is1The group being-CH2CH2-、
Figure FDA0003002627190000012
Figure FDA0003002627190000013
R3The group being-CH3、-CH2CH2CH3、-CH(CH3)2、-CH2Ph。
2. A process for the preparation of hydroxycarborane derivatives containing ether linkages as claimed in claim 1, which comprises the steps of:
(1) under the condition of inert gas atmosphere at-60 to-20 ℃, dropwise adding a hexane solution of n-butyllithium into an ether solution of o-carborane, and stirring for 10-30 min; adding an ether solution of formate into the system, raising the temperature to 0-50 ℃, and continuing to stir for 4-24 h, or adding an ether solution of a halogenated dioxolane compound into the system, raising the temperature to 0-50 ℃, continuing to stir for 4-24 h, and then adding methyl p-toluenesulfonate and continuing to stir for 1-4 h; adding a quenching agent to carry out quenching reaction, extracting the water phase by using ether, collecting the organic phase, and carrying out rotary evaporation on the organic phase to remove the residual solvent to obtain o-carborane B-1 containing a single aldehyde group;
(2) dissolving B-1 in a methanol solution, adding a reducing agent at the temperature of-10 ℃, stirring for reaction for 2-8 h, filtering and discharging, and performing rotary evaporation on a product to obtain o-carborane B-2 containing monohydroxy groups;
(3) under the alkaline condition, B-2 and epoxide react under stirring at 40-80 ℃ to obtain the hydroxyl carborane derivative containing ether bond.
3. The method for preparing the ether bond-containing hydroxycarborane derivative modified curing agent according to claim 1, wherein a molar ratio of n-butyllithium to o-carborane in the step (1) is 1-1.3: 1.
4. The method for preparing the ether bond-containing hydroxycarborane derivative-modified curing agent according to claim 1, wherein the halogenated dioxolane compound in the step (1) is one or more selected from the group consisting of 2- (2-bromoethyl) -1, 3-dioxolane, 2-bromobenzaldehyde vinylaldehyde, 2- (2-bromo-5-methoxyphenyl) - [1,3] dioxolane, and 2- (2-bromophenoxymethyl) - [1,3] dioxolane; the formate in the step (1) is methyl formate.
5. The method for preparing the ether linkage-containing hydroxycarborane derivative modified curing agent according to claim 1, wherein the ether in the step (1) is one or more of ethyl ether, propyl ether or dibutyl ether; the quenching agent is one or more of dilute acetic acid solution and dilute hydrochloric acid solution;
in the step (2), the reducing agent is one or more of hydrogen, sodium borohydride, lithium aluminum hydride and diborane.
6. The method for preparing the ether linkage-containing hydroxycarborane derivative-modified curing agent according to claim 1, wherein the epoxide in the step (3) is one or more selected from the group consisting of propylene oxide, propylethylene oxide, 2-isobutylethylene oxide, and 2-benzylethylene oxide; and (3) the alkaline environment is an ethylenediamine solution.
7. A preparation method of hydroxyl carborane derivative modified curing agent containing ether bond is characterized by comprising the following steps:
dropwise adding the hydroxyl carborane derivative containing ether bonds in the isocyanate curing agent at 40-80 ℃, keeping the temperature, continuously stirring and reacting for 40-60 min, cooling and discharging to obtain the hydroxyl carborane derivative modified curing agent containing ether bonds.
8. The method of claim 7, wherein the isocyanate curing agent comprises TDI-TMP adduct, TDI trimer curing agent or HDI trimer curing agent.
9. The modified curing agent of hydroxycarborane derivative containing ether bond prepared by the method of any one of claims 7 to 8.
10. Use of a hydroxycarborane derivative modified curing agent containing an ether linkage as defined in claim 9 to improve paint film properties.
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