CN108822011A - A kind of preparation method of polythiol curing agent - Google Patents
A kind of preparation method of polythiol curing agent Download PDFInfo
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- CN108822011A CN108822011A CN201810684687.3A CN201810684687A CN108822011A CN 108822011 A CN108822011 A CN 108822011A CN 201810684687 A CN201810684687 A CN 201810684687A CN 108822011 A CN108822011 A CN 108822011A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/30—Isothioureas
- C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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Abstract
The present invention provides a kind of preparation methods of polythiol curing agent, including：A) under the action of phase transfer catalyst, chloride polyether polyol shown in formula (1) is reacted in aqueous solution with thiocarbamide, obtains intermediate；B) intermediate and alkaline matter are subjected to Basic fluxing raction, polythiol shown in production (2)；Wherein, R is selected fromWith
Description
Technical field
The present invention relates to technical field of organic synthesis, in particular to a kind of preparation method of polythiol curing agent.
Background technique
Epoxy resin can be used as the construction structure glue of function admirable with after curing agent cross-linking reaction, be current building knot
Apply most glue classes in structure glue field.And common epoxy curing agent is difficult to solidify at temperature lower (15 DEG C of <), limit
The application of its winter is made.
Currently, a kind of method for solving the problems, such as low-temperature setting is modified fatty amine, active group is introduced into fatty amine, with
Epoxy resin can react solidification at low temperature；Another method is then using thio-alcohol curing agent.Thio-alcohol curing agent is one
Kind neo-epoxy resin curing agent, end group have more than two sulfydryls, can be used as active group and react with cross linking of epoxy resin,
Compared with other epoxy hardeners, solidification low with solidification temperature rapidly, thin layer solidification and solidify of light color etc. significant excellent
Point is that other curing agent are irreplaceable, therefore its demand increasingly increases, and therefore, the production preparation of polythiol curing agent has
Very great meaning.
In the prior art, the method for preparing polythiol curing agent mainly has NaHS nucleophilic method, using NaHS original
Material synthesis polythiol；However, this method, there are apparent defect, side reaction is difficult to control, the thioether that side reaction generates is not only
Making the active group sulfhydryl content of polythiol reduces, and also greatly increases product viscosity；In addition, raw material NaHS smell is big,
The waste water of generation is difficult to handle, and the more difficult storage of NaHS, and easily jaundice is rotten after contacting with the air, influences the product of sintetics
Matter.
In order to solve the above problem, researcher proposes to prepare polythiol using Thiourea-uv Method, that is, abandons NaHS and adopt
The synthesis of polythiol is carried out with thiocarbamide.Although however, theoretically propose the substantially synthetic route for preparing polythiol using thiocarbamide,
But it is rarely reported about its detailed preparation process, because it is difficult to react in actual fabrication process, reaction is difficult to occur
With go on smoothly, it is more difficult to obtain high sulfhydryl content product.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation methods of polythiol curing agent, using of the invention
Preparation method can successfully realize that thiocarbamide prepares polythiol, and can obtain high sulfhydryl content product.
The present invention provides a kind of preparation methods of polythiol curing agent, include the following steps：
A) under the action of phase transfer catalyst, chloride polyether polyol shown in formula (1) and thiocarbamide is anti-in aqueous solution
It answers, obtains intermediate；
B) intermediate and alkaline matter are subjected to Basic fluxing raction, polythiol shown in production (2)；
Wherein, R is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；
The phase transfer catalyst is selected from one or more of quaternary ammonium compound and quaternary phosphonium salt class compound.
Preferably, the quaternary ammonium compound is selected from 4-butyl ammonium hydrogen sulfate, dodecyl trimethyl ammonium chloride, phenyl
One or more of trimethoxy ammonium chloride and benzyltriethylammoinium chloride；
The quaternary phosphonium salt class compound is selected from four (diethylin) bromide phosphines and three (piperidyls)-(diethylin) bromide phosphine
One or more of.
Preferably, in the step a), the molar ratio of hydroxyl is (0.5 in chloride polyether polyol shown in thiocarbamide and formula (1)
~3.0): 1.
Preferably, in the step a), the mass ratio of phase transfer catalyst and chloride polyether polyol shown in formula (1) is
(0.01~50): 100.
Preferably, the temperature reacted in the step a) is 30~90 DEG C.
Preferably, in chloride polyether polyol shown in the alkaline matter and formula (1) molar ratio of hydroxyl be (0.5~
3.0)∶1。
Preferably, the alkaline matter is selected from one or more of potassium hydroxide, sodium hydroxide, carbonate and ammonium hydroxide.
Preferably, in the step b), the temperature of Basic fluxing raction is 30~90 DEG C, and the time is 2~8 hours.
Preferably, chloride polyether polyol shown in formula (1) obtains in the following manner：
Under the action of catalyst, by polyether polyol and epichlorohydrin reaction shown in formula (3), chlorine shown in formula (1) is obtained
For polyether polyol；
Wherein, it is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；
The catalyst is lewis acid catalyst.
Preferably, the molar ratio of epoxychloropropane and hydroxyl in polyether polyol shown in formula (3) is (0.5~3.0): 1；
The mass ratio of polyether polyol shown in catalyst and formula (3) is (0.01~50): 100.
The present invention provides a kind of preparation methods of polythiol curing agent, including：A) under the action of phase transfer catalyst,
Chloride polyether polyol shown in above-mentioned formula (1) is reacted in aqueous solution with thiocarbamide, obtains intermediate；B) by the intermediate with
Alkaline matter carries out Basic fluxing raction, polythiol shown in production (2)；Wherein, R is selected fromWithIn
One kind；The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；The phase transfer catalyst is selected from
One or more of quaternary ammonium compound and quaternary phosphonium salt class compound.Preparation method of the invention can successfully be prepared more
Mercaptan overcomes Thiourea-uv Method and is difficult to the problem of generating polythiol, and obtains high sulfhydryl content product, and product coloration is good.
Experiment results proved, sulfhydryl content reaches 11% or more in polythiol product produced by the present invention, and product is nothing
Color is transparent, shows preferable coloration.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the infrared spectrum of 1 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of polythiol curing agent, which is characterized in that includes the following steps：
A) under the action of phase transfer catalyst, chloride polyether polyol shown in formula (1) and thiocarbamide is anti-in aqueous solution
It answers, obtains intermediate；
B) intermediate and alkaline matter are subjected to Basic fluxing raction, polythiol shown in production (2)；
Wherein, R is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；
The phase transfer catalyst is selected from one or more of quaternary ammonium compound and quaternary phosphonium salt class compound.
Preparation method provided by the invention, by chloride polyether polyol shown in formula (1) and thiocarbamide in specific phase transfer catalysis (PTC)
Under agent effect, reacts in water, carry out alkaline hydrolysis again later, thus polythiol shown in production (2).Preparation side of the invention
Method can successfully prepare polythiol, overcome Thiourea-uv Method and be difficult to the problem of generating polythiol, and obtain high sulfhydryl content
Product, experiment results proved, sulfhydryl content reaches 11% or more in polythiol product produced by the present invention.
According to the present invention, first under the action of phase transfer catalyst, by chloride polyether polyol and thiocarbamide shown in formula (1)
It reacts in aqueous solution, obtains intermediate.
In the present invention, the structure of chloride polyether polyol shown in the formula (1) is as follows：
Wherein, R is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously.Preferably, p, m and n are not
0。
In the present invention, chloride polyether polyol shown in the formula (1) preferably obtains in the following manner：
Under the action of catalyst, by polyether polyol and epichlorohydrin reaction shown in formula (3), chlorine shown in formula (1) is obtained
For polyether polyol；
Wherein, it is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously.
The source of polyether polyol shown in the formula (3) is not particularly limited, for general commercially available product or according to this field skill
Preparation method known to art personnel is made.In polyether polyol shown in formula (3), preferably, p, m and n are not 0.Institute
The source for stating epoxychloropropane is not particularly limited, and is general commercially available product.Polyethers shown in the epoxychloropropane and formula (3)
The molar ratio of hydroxyl is preferably (0.5~3.0): 1, more preferably (1.0~2.5): 1 in polyalcohol.
The catalyst is preferably lewis acid catalyst, the tin based compound catalyst more preferably in lewis acid and
Borate compounds catalyst；In one embodiment, catalyst is boron trifluoride；In another embodiment, catalyst three
Boron fluoride 5H2O.The mass ratio of polyether polyol shown in the catalyst and formula (3) is preferably (0.01~50): 100, it is more excellent
It is selected as (1~40): 100, further preferably (10~30): 100.
In mixed raw material, preferably mix in the following manner：It is first that polyether polyol shown in formula (3) and catalyst is mixed
It closes, is warming up to reaction temperature, then epoxychloropropane is slowly added dropwise.Polyether polyol shown in formula (3) and epoxychloropropane are being catalyzed
When being reacted under the action of agent, the temperature of reaction is preferably 30~90 DEG C, and more preferably 70~80 DEG C.The time of reaction is preferred
For 0.5~2.5h.After the reaction, chloride polyether polyol shown in formula (1) is obtained.
In the present invention, reacted using thiocarbamide with chloride polyether polyol shown in above-mentioned formula (1).The present invention is to the sulphur
The source of urea is not particularly limited, and is general commercially available product.In the present invention, chloride polyether polyol shown in thiocarbamide and formula (1)
The molar ratio of middle hydroxyl is preferably (0.5~3.0): 1.
In the present invention, thiocarbamide reacts in an aqueous medium with chloride polyether polyol shown in above-mentioned formula (1), and thiocarbamide is in water
Mass concentration is preferably 10%~90%, and more preferably 50%~80%, further preferably 70%~80%.In the present invention,
The aqueous medium can be introduced by way of thiourea solution, i.e., by chloride polyether polyol shown in thiourea solution and formula (1)
Mixing is reacted.
In the present invention, chloride polyether polyol shown in thiocarbamide and formula (1) needs the effect in specific phase transfer catalyst
Lower just to react, the phase transfer catalyst is selected from one of quaternary ammonium compound and quaternary phosphonium salt class compound or several
Kind.In some embodiments, the quaternary ammonium compound be selected from 4-butyl ammonium hydrogen sulfate, dodecyl trimethyl ammonium chloride,
One or more of phenyl trimethoxy ammonium chloride and benzyltriethylammoinium chloride；In further embodiments, the season phosphine
Salt compounds are selected from one or more of four (diethylin) bromide phosphines and three (piperidyls)-(diethylin) bromide phosphine.
In the present invention, the phase transfer catalyst is preferably 4-butyl ammonium hydrogen sulfate.By adding above-mentioned phase transfer catalyst, can promote
Thiocarbamide reacts to form isothiuronium salts with formula (1) chloride polyether polyol, and then successfully obtains polythiol product.
In the present invention, the mass ratio of chloride polyether polyol shown in the phase transfer catalyst and formula (1) is preferably (0.01
~50): 100, more preferably (1~40): 100, further preferably (10~30): 100.
In the present invention, the temperature that chloride polyether polyol shown in formula (1) is reacted with thiocarbamide is preferably 30~90 DEG C；Described
In temperature range, is conducive to generate polythiol and obtains good coloration, if temperature is lower than 30 DEG C, be difficult to generate polythiol, if
Temperature is higher than 90 DEG C, then easily crosslinks and xanthochromia.In the present invention, the time of the reaction is preferably at 3 hours or more.Described
After reaction, isothiuronium salts intermediate is obtained.
According to the present invention, after obtaining intermediate, the intermediate and alkaline matter are subjected to Basic fluxing raction, production
(2) polythiol shown in.
In the present invention, the alkaline matter is preferably one of potassium hydroxide, sodium hydroxide, carbonate and ammonium hydroxide or several
Kind.The carbonate is preferably one or more of sodium carbonate, potassium carbonate and ammonium carbonate.The present invention utilizes alkaline matter centering
Mesosome carries out alkaline hydrolysis, makes isothiuronium salts intermediate scission of link, to form polythiol.
In the present invention, in chloride polyether polyol shown in the alkaline matter and formula (1) molar ratio of hydroxyl be (0.5~
3.0):1；It help to obtain polythiol product in the proportional region, if alkali number is too low, easily leads to alkaline hydrolysis and is not thorough, remains
A large amount of macromolecular salts influence product quality and generate a large amount of sulphur anions, high activity sulphur anion can be fast if alkali number is excessively high
Speed is oxidized to two thio impurity, to influence the acquisition of polythiol product.
In the present invention, alkaline matter preferably introduces in the form of a solution, i.e., intermediate is mixed to progress with alkaline substance solution
Basic fluxing raction.The mass concentration of the alkaline substance solution is preferably 10%~30%.
In the present invention, the temperature of the Basic fluxing raction is preferably 30~90 DEG C；In the temperature range, be conducive to generate
Polythiol simultaneously obtains good coloration, if temperature is lower than 30 DEG C, is difficult to generate polythiol, if temperature is higher than 90 DEG C, easily occurs
Crosslinking and xanthochromia.In the present invention, the time of the Basic fluxing raction is preferably at 2~8 hours.
In the present invention, after the Basic fluxing raction, preferably also post-processed；The post-processing preferably includes pickling, water
It washes and dries.In the present invention, after Basic fluxing raction, obtained material layering, upper layer is oil phase substance, and the present invention is preferably by oil phase thing
Matter is cut out, and then uses the pH value of acid solution regulation system；The present invention preferably adjusts pH value to 5~6.The type of the acid solution is without spy
System PH, can be adjusted to 5~6 by different limitation, in one embodiment, adjust PH using dilute hydrochloric acid.In above-mentioned pickling
Afterwards, it is preferably also washed, is washed to neutrality.The water that the washing uses is preferably deionized water；The temperature of the washing
It spends preferably identical as Basic fluxing raction temperature.After the washing, preferably it is dried；The mode of the drying does not have special limit
System, moisture can be removed, in one embodiment, remove water drying by revolving mode.
After above-mentioned post-processing, polythiol is obtained；The polythiol has structure shown in formula (2)：
Wherein, R is selected fromWithOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously.Preferably, p, m and n are not
0。
Preparation method of the invention can successfully prepare polythiol, overcome Thiourea-uv Method and be difficult to generate asking for polythiol
Topic, and obtains high sulfhydryl content product, experiment results proved, and sulfhydryl content reaches in polythiol product produced by the present invention
11% or more.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
3 compound (p of 40.00g (0.159mol hydroxyl) formula is added into the 100mL four-hole bottle equipped with thermometer, blender
=1, m=1, n=1, R 1) and 4.8g boron trifluoride, it opens and is stirred and heated to 70 DEG C, 19.22g is slowly added dropwise at 70 DEG C
(0.207mol) epoxychloropropane, keeps the temperature 1h at 70 DEG C after being added dropwise, and obtains among the pale yellow transparent with 1 structure of formula
Body 59.34g.
It is 80% thiourea solution (containing thiocarbamide that 8.90g 4-butyl ammonium hydrogen sulfate and concentration are continuously added into system
20.26g, 0.269mol), 3h is stirred to react at 70 DEG C；The sodium carbonate liquor that 123.08g concentration is 25% is added later (to contain
Sodium carbonate 0.290mol), 2h is stirred to react at 70 DEG C；Upper oil phase is cut out, adjusts pH value to 5~6, then with dilute hydrochloric acid
It is washed with 40.00g70 DEG C of deionized water, then rotates water removal, obtain colorless and transparent polythiol.
IR Characterization test is carried out to gained polythiol product, as a result as shown in FIG. 1, FIG. 1 is the present embodiment products obtained therefroms
Infrared spectrum, display products obtained therefrom have formula 2 shown in structure.After tested, the sulfhydryl content in product is 12.78%.
Embodiment 2
3 compound (p of 40.00g (0.159mol hydroxyl) formula is added into the 100mL four-hole bottle equipped with thermometer, blender
=1, m=1, n=1, R 1) and 4.8g boron trifluoride 5H2O, unlatching are stirred and heated to 70 DEG C, are slowly added dropwise at 70 DEG C
17.74g (0.191mol) epoxychloropropane, keeps the temperature 1h at 70 DEG C after being added dropwise, and obtains having the faint yellow of 1 structure of formula
Bright intermediate 57.86g.
It is 80% thiourea solution (containing thiocarbamide that 8.68g 4-butyl ammonium hydrogen sulfate and concentration are continuously added into system
18.86g, 0.248mol), 3h is stirred to react at 70 DEG C；The sodium carbonate liquor that 113.32g concentration is 25% is added later (to contain
Sodium carbonate 0.267mol), 2h is stirred to react at 70 DEG C；Upper oil phase is cut out, adjusts pH value to 5~6, then with dilute hydrochloric acid
It is washed with 40.00g70 DEG C of deionized water, then rotates water removal, obtain colorless and transparent polythiol.
Characterization test is carried out to gained polythiol product according to the test method of embodiment 1, the results show that it is with formula 2
Shown structure, sulfhydryl content 11.92%.
Embodiment 3
3 compound (p of 40.00g (0.159mol hydroxyl) formula is added into the 100mL four-hole bottle equipped with thermometer, blender
=1, m=1, n=1, R 1) and 4.8g boron trifluoride 5H2O, unlatching are stirred and heated to 70 DEG C, are slowly added dropwise at 70 DEG C
19.22g (0.207mol) epoxychloropropane, keeps the temperature 1h at 70 DEG C after being added dropwise, and obtains having the faint yellow of 1 structure of formula
Bright intermediate 59.34g.
It is 80% thiourea solution (containing thiocarbamide that 11.87g 4-butyl ammonium hydrogen sulfate and concentration are continuously added into system
20.46g, 0.269mol), 3h is stirred to react at 70 DEG C；The sodium carbonate liquor that 123.08g concentration is 25% is added later (to contain
Sodium carbonate 0.290mol), 2h is stirred to react at 70 DEG C；Upper oil phase is cut out, adjusts pH value to 5~6, then with dilute hydrochloric acid
It is washed with 40.00g70 DEG C of deionized water, then rotates water removal, obtain colorless and transparent polythiol.
Characterization test is carried out to gained polythiol product according to the test method of embodiment 1, the results show that it is with formula 2
Shown structure, sulfhydryl content 12.90%.
Embodiment 4
3 compound (p of 40.00g (0.159mol hydroxyl) formula is added into the 100mL four-hole bottle equipped with thermometer, blender
=1, m=1, n=1, R 1) and 4.8g boron trifluoride 5H2O, unlatching are stirred and heated to 70 DEG C, are slowly added dropwise at 70 DEG C
19.22g (0.207mol) epoxychloropropane, keeps the temperature 1h at 70 DEG C after being added dropwise, and obtains having the faint yellow of 1 structure of formula
Bright intermediate 59.34g.
It is 80% thiourea solution (containing thiocarbamide that 5.93g 4-butyl ammonium hydrogen sulfate and concentration are continuously added into system
20.46g, 0.269mol), 3h is stirred to react at 70 DEG C；The sodium carbonate liquor that 123.08g concentration is 25% is added later (to contain
Sodium carbonate 0.290mol), 2h is stirred to react at 70 DEG C；Upper oil phase is cut out, adjusts pH value to 5~6, then with dilute hydrochloric acid
It is washed with 40.00g70 DEG C of deionized water, then rotates water removal, obtain colorless and transparent polythiol.
Characterization test is carried out to gained polythiol product according to the test method of embodiment 1, the results show that it is with formula 2
Shown structure, sulfhydryl content 12.46%.
Embodiment 5
3 compound (p of 40.00g (0.159mol hydroxyl) formula is added into the 100mL four-hole bottle equipped with thermometer, blender
=1, m=1, n=1, R 1) and 4.8g boron trifluoride 5H2O, unlatching are stirred and heated to 70 DEG C, are slowly added dropwise at 70 DEG C
19.22g (0.207mol) epoxychloropropane, keeps the temperature 1h at 70 DEG C after being added dropwise, and obtains having the faint yellow of 1 structure of formula
Bright intermediate 59.34g.
It is 80% thiourea solution (containing thiocarbamide that 8.68g 4-butyl ammonium hydrogen sulfate and concentration are continuously added into system
20.46g, 0.269mol), 3h is stirred to react at 70 DEG C；The sodium carbonate liquor that 123.08g concentration is 25% is added later (to contain
Sodium carbonate 0.290mol), 2h is stirred to react at 70 DEG C；Upper oil phase is cut out, adjusts pH value to 5~6, then with dilute hydrochloric acid
It is washed with 40.00g70 DEG C of deionized water, then rotates water removal, obtain colorless and transparent polythiol.
Characterization test is carried out to gained polythiol product according to the test method of embodiment 1, the results show that it is with formula 2
Shown structure, sulfhydryl content 12.52%.
Embodiment 6
It is carried out according to the preparation process of embodiment 1, unlike, phase transfer catalyst is replaced with into trimethyl
Ammonium chloride obtains colorless and transparent product.Products obtained therefrom is tested according to the test side of embodiment 1, the results show that gained produces
Product are the polythiol with 2 structure of formula, sulfhydryl content 12.19%.
Embodiment 7
It is carried out according to the preparation process of embodiment 2, unlike, phase transfer catalyst is replaced with into phenyl trimethoxy chlorine
Change ammonium, obtains colorless and transparent product.Products obtained therefrom is tested according to the test side of embodiment 1, the results show that products obtained therefrom
For the polythiol with 2 structure of formula, sulfhydryl content 12.08%.
Embodiment 8
It is carried out according to the preparation process of embodiment 3, unlike, phase transfer catalyst is replaced with into benzyl triethyl ammonium chlorination
Ammonium obtains colorless and transparent product.Products obtained therefrom is tested according to the test side of embodiment 1, the results show that products obtained therefrom is
Polythiol with 2 structure of formula, sulfhydryl content 12.25%.
Embodiment 9
It is carried out according to the preparation process of embodiment 4, unlike, phase transfer catalyst is replaced with into four (diethylin) bromines
Change phosphine, obtains colorless and transparent product.Products obtained therefrom is tested according to the test side of embodiment 1, the results show that products obtained therefrom
For the polythiol with 2 structure of formula, sulfhydryl content 11.88%.
Embodiment 10
It is carried out according to the preparation process of embodiment 5, unlike, phase transfer catalyst is replaced with into three (piperidyl)-(two
Ethylamino-) bromide phosphine, obtain colorless and transparent product.Products obtained therefrom is tested according to the test side of embodiment 1, is as a result shown
Show, products obtained therefrom is the polythiol with 2 structure of formula, sulfhydryl content 11.74%.
As seen from the above embodiment, preparation method provided by the invention can prepare polythiol product, and product mercapto
Base content is high, and coloration is transparent.
Comparative example 1
It is carried out according to the preparation process of embodiment 1, unlike, phase transfer catalyst is replaced with into polyethylene glycol.According to
The test side of embodiment 1 tests products obtained therefrom, the results show that products obtained therefrom is high viscosity jaundice liquid, sulfhydryl content
Only 9.42%.
It follows that can not also obtain high sulfhydryl content when phase transfer catalyst is replaced with other similar catalyst
Polythiol product could obtain high-quality polythiol under specific phase transfer catalyst effect provided by the invention.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field is appointed
What technical staff can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementations
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, are wanted then these other embodiments should also be included in right
In the range of asking.
Claims (10)
1. a kind of preparation method of polythiol curing agent, which is characterized in that include the following steps：
A) under the action of phase transfer catalyst, chloride polyether polyol shown in formula (1) is reacted in aqueous solution with thiocarbamide, is obtained
To intermediate；
B) intermediate and alkaline matter are subjected to Basic fluxing raction, polythiol shown in production (2)；
Wherein, R is selected fromOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；
The phase transfer catalyst is selected from one or more of quaternary ammonium compound and quaternary phosphonium salt class compound.
2. preparation method according to claim 1, which is characterized in that the quaternary ammonium compound is selected from tetrabutyl sulfuric acid
One or more of hydrogen ammonium, dodecyl trimethyl ammonium chloride, phenyl trimethoxy ammonium chloride and benzyltriethylammoinium chloride；
The quaternary phosphonium salt class compound is selected from four (diethylin) bromide phosphines and three (piperidyls)-(diethylin) bromide phosphine
It is one or more of.
3. preparation method according to claim 1, which is characterized in that in the step a), chloro shown in thiocarbamide and formula (1)
The molar ratio of hydroxyl is (0.5~3.0) in polyether polyol: 1.
4. preparation method according to claim 1 or 3, which is characterized in that in the step a), phase transfer catalyst and formula
(1) mass ratio of chloride polyether polyol shown in is (0.01~50): 100.
5. preparation method according to claim 1, which is characterized in that the temperature reacted in the step a) is 30~90
℃。
6. preparation method according to claim 1, which is characterized in that chloro polyethers shown in the alkaline matter and formula (1)
The molar ratio of hydroxyl is (0.5~3.0) in polyalcohol: 1.
7. preparation method according to claim 1 or 5, which is characterized in that the alkaline matter is selected from potassium hydroxide, hydrogen-oxygen
Change one or more of sodium, carbonate and ammonium hydroxide.
8. preparation method according to claim 1, which is characterized in that in the step b), the temperature of Basic fluxing raction is 30
~90 DEG C, the time is 2~8 hours.
9. preparation method according to claim 1, which is characterized in that chloride polyether polyol shown in formula (1) passes through following
Mode obtains：
Under the action of catalyst, by polyether polyol and epichlorohydrin reaction shown in formula (3), it is poly- to obtain chloro shown in formula (1)
Ethoxylated polyhydric alcohol；
Wherein, it is selected fromOne of；
The degree of polymerization p, m and n are independently selected from 0~5, and p, m and n are not 0 simultaneously；
The catalyst is lewis acid catalyst.
10. preparation method according to claim 9, which is characterized in that polyether polyol shown in epoxychloropropane and formula (3)
The molar ratio of middle hydroxyl is (0.5~3.0): 1；
The mass ratio of polyether polyol shown in catalyst and formula (3) is (0.01~50): 100.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180926A (en) * | 2018-11-28 | 2019-01-11 | 山东益丰生化环保股份有限公司 | A kind of preparation method of polyether-type multi-thioalcohol compound |
| CN110452370A (en) * | 2019-08-26 | 2019-11-15 | 山东益丰生化环保股份有限公司 | A kind of polysulfide alcohols curing agent and its preparation method and application |
| CN112300370A (en) * | 2020-08-05 | 2021-02-02 | 山东益丰生化环保股份有限公司 | Viscosity-controllable polythiol epoxy resin curing agent and preparation method thereof |
| WO2021114920A1 (en) * | 2019-12-13 | 2021-06-17 | 山东益丰生化环保股份有限公司 | Catalyst for preparing polythiol curing agent and use thereof |
| WO2023054459A1 (en) | 2021-09-29 | 2023-04-06 | 東レ・ファインケミカル株式会社 | Production method of thiol group-containing polyether polymer |
| CN117343477A (en) * | 2023-09-28 | 2024-01-05 | 益丰新材料股份有限公司 | Curable composition and application thereof |
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2018
- 2018-06-28 CN CN201810684687.3A patent/CN108822011A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 王安亭: "多硫醇快速固化剂的合成", 《热固性树脂》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180926A (en) * | 2018-11-28 | 2019-01-11 | 山东益丰生化环保股份有限公司 | A kind of preparation method of polyether-type multi-thioalcohol compound |
| CN110452370A (en) * | 2019-08-26 | 2019-11-15 | 山东益丰生化环保股份有限公司 | A kind of polysulfide alcohols curing agent and its preparation method and application |
| CN110452370B (en) * | 2019-08-26 | 2020-10-20 | 山东益丰生化环保股份有限公司 | Polythiol curing agent, and preparation method and application thereof |
| WO2021114920A1 (en) * | 2019-12-13 | 2021-06-17 | 山东益丰生化环保股份有限公司 | Catalyst for preparing polythiol curing agent and use thereof |
| CN112300370A (en) * | 2020-08-05 | 2021-02-02 | 山东益丰生化环保股份有限公司 | Viscosity-controllable polythiol epoxy resin curing agent and preparation method thereof |
| WO2023054459A1 (en) | 2021-09-29 | 2023-04-06 | 東レ・ファインケミカル株式会社 | Production method of thiol group-containing polyether polymer |
| CN117343477A (en) * | 2023-09-28 | 2024-01-05 | 益丰新材料股份有限公司 | Curable composition and application thereof |
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