CN107936217A - A kind of synthetic method of sulfur-containing polymer polyalcohol - Google Patents
A kind of synthetic method of sulfur-containing polymer polyalcohol Download PDFInfo
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- CN107936217A CN107936217A CN201711192792.7A CN201711192792A CN107936217A CN 107936217 A CN107936217 A CN 107936217A CN 201711192792 A CN201711192792 A CN 201711192792A CN 107936217 A CN107936217 A CN 107936217A
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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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
- C09D175/08—Polyurethanes from polyethers
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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
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
By Thiodiglycol, 2 hydroxypropyl sulphide of ethoxy etc. it is primary raw material the invention discloses one kind, using acidic catalyst, carry out hydroxyls dehydrate polycondensation reaction, by control reaction process and effective post processing synthesis suitable viscosity, suitable molecular weight sulfur-containing polymer polyalcohol method.Contain more monosulfidic bond in product backbone structure, manufactured polyurethane material has good oil resistant, ageing-resistant, heat resistance.Raw material is cheap and easily-available, and reacting balance, product quality is easy to control, and the sulfur-containing polymer polyol viscosity of generation is moderate, and stability is good.
Description
Technical field
The invention belongs to high molecular polymer production technical field, and in particular to the synthesis side of sulfur-containing polymer polyalcohol
Method.
Background technology
Sulfur-containing polymer polyalcohol refers to a kind of aliphatic saturated polymer containing monosulfidic bond in molecular backbone, and the U.S. is most
Early industrialized production, sulfur-containing polymer polyalcohol be used for polyurethane material raw material, can improve polyurethane material solvent resistant,
Resistance to fuel oil, chemical resistance, receive in anticorrosive paint, sealing material and are widely used.
At present, the domestic report without sulfur-containing polymer polyalcohol study on the synthesis.
The present invention is used using Thiodiglycol, ethoxy -2- hydroxypropyl sulphides as the synthetic route of main monomer, synthesizes sulfur-bearing
Polymer polyatomic alcohol, reacting balance, product quality are easy to control, and raw material is cheap and easily-available.
The content of the invention
Synthesized it is an object of the invention to provide one kind using Thiodiglycol, ethoxy -2- hydroxypropyl sulphides as main monomer
The process route of sulfur-containing polymer polyalcohol.Using acidic catalyst, carry out hydroxyls dehydrate polycondensation reaction, by control react into
Journey and effective post processing, synthesis suitable viscosity, the sulfur-containing polymer polyalcohol of suitable molecular weight.Reacting balance, product quality
It is easy to control, raw material is cheap and easily-available, and the sulfur-containing polymer polyol viscosity of generation is moderate, even molecular weight distribution.Because of product master
Contain more monosulfidic bond in chain structure, can be made into special polyurethane material, there is good oil resistant, ageing-resistant, heat resistance.
The invention discloses a kind of synthetic method of sulfur-containing polymer polyalcohol, comprise the following steps：
Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, trimethylolpropane is used according to a certain ratio, to be urged for raw material
After lower 160~190 DEG C of agent effect carries out 5~8h of dehydrating polycondensation reaction, reaction 2~4h (overbottom pressure is vacuumized at this temperature
Below 20mmHg), the reaction product of polycondensation reaction is after unreacted small-molecule substance is removed in solvent extraction, at 120~160 DEG C,
Below overbottom pressure 2.66kPa carries out 2~5h of vacuum reaction, obtains sulfur-containing polymer polyalcohol.
In the synthetic reaction of sulfur-containing polymer polyalcohol of the present invention, Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, three
The molar ratio of hydroxymethyl-propane is 0.32 ﹕ 0.030 of 1 ﹕ 0.25~0.45 ﹕ 0.025~0.045, preferably 1 ﹕；The catalyst is to first
The dosage of benzene sulfonic acid is 0.5~2.0% (mass parts) of Thiodiglycol dosage, preferably.
In the synthetic reaction of sulfur-containing polymer polyalcohol of the present invention, Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, three
The dehydration temperature of hydroxymethyl-propane reaction is 160~190 DEG C, preferably 170 DEG C.
In the synthetic reaction of sulfur-containing polymer polyalcohol of the present invention, Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, three
After the polycondensation reaction time of hydroxymethyl-propane is 5~8h, 2~4h of reaction (below overbottom pressure 2.66kPa) is vacuumized, preferably polycondensation is anti-
It is after 7h between seasonable, vacuumizes reaction 2.5h.
In the synthetic reaction of sulfur-containing polymer polyalcohol of the present invention, Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, three
The reaction product of the polycondensation reaction of hydroxymethyl-propane is after unreacted small-molecule substance is removed in solvent extraction, at 120~160 DEG C,
Below overbottom pressure 2.66kPa carries out 2~5h of vacuum reaction, preferably 140 DEG C of vacuum reaction 4h.
Its structural formula is：
Beneficial effect of the present invention is to use Thiodiglycol, ethoxy -2- hydroxypropyl sulphides for main monomer synthesis to contain
Sulphur polymer polyatomic alcohol, reacting balance, product quality are easy to control, and raw material is cheap and easily-available, due to containing in product backbone structure
More monosulfidic bond, can be made into special polyurethane material, have good oil resistant, ageing-resistant, heat resistance, be applied in heavy antisepsis
The fields such as material, sealing material are applied.The raw materials such as Thiodiglycol that the present invention uses, ethoxy -2- hydroxypropyl sulphides are
Jinxi Research Institute of Chemical Industry Co., Ltd. makes by oneself.
Embodiment
Embodiment 1
Equipped with blender, thermometer, condenser, low molecule receiver 5L stainless steel cauldrons in, load 2.0kg sulphur
For diethylene glycol (DEG), 0.71kg ethoxy -2- hydroxypropyl sulphides, 68.6g trimethylolpropanes, 22.0g p-methyl benzenesulfonic acid, it is warming up to
170 DEG C, after 170 ± 2 DEG C of controlling reaction temperature reacts 7h, at this temperature, below overbottom pressure 2.66kPa is controlled, it is anti-to carry out vacuum
2.5h is answered, the reaction product ethanol extraction of polycondensation reaction then is removed unreacted small-molecule substance obtains crude product, and crude product is 140
DEG C, below overbottom pressure 2.66kPa carries out vacuum reaction 4h, obtains sulfur-containing polymer polyalcohol.Hydroxyl value 56.8mg KOH/g, viscosity
28Pa·s。
Embodiment 2
Equipped with blender, thermometer, condenser, low molecule receiver 5L stainless steel cauldrons in, load 2.0kg sulphur
For diethylene glycol (DEG), 0.71kg ethoxy -2- hydroxypropyl sulphides, 68.6g trimethylolpropanes, 40.0g p-methyl benzenesulfonic acid, it is warming up to
170 DEG C, after 170 ± 2 DEG C of controlling reaction temperature reacts 7h, at this temperature, below overbottom pressure 2.66kPa is controlled, it is anti-to carry out vacuum
2.5h is answered, the reaction product ethanol extraction of polycondensation reaction then is removed unreacted small-molecule substance obtains crude product, and crude product is 140
DEG C, below overbottom pressure 2.66kPa carries out vacuum reaction 4h, obtains sulfur-containing polymer polyalcohol.Hydroxyl value 38.4mg KOH/g, viscosity
37Pa·s。
Embodiment 3
Equipped with blender, thermometer, condenser, low molecule receiver 5L stainless steel cauldrons in, load 2.0kg sulphur
For diethylene glycol (DEG), 0.71kg ethoxy -2- hydroxypropyl sulphides, 68.6g trimethylolpropanes, 22.0g p-methyl benzenesulfonic acid, it is warming up to
170 DEG C, after 170 ± 2 DEG C of controlling reaction temperature reacts 7h, at this temperature, below overbottom pressure 2.66kPa is controlled, it is anti-to carry out vacuum
4h is answered, the reaction product ethanol extraction of polycondensation reaction then is removed unreacted small-molecule substance obtains crude product, and crude product is 140
DEG C, below overbottom pressure 2.66kPa carries out vacuum reaction 4h, obtains sulfur-containing polymer polyalcohol.Hydroxyl value 39.9mg KOH/g, viscosity
39.5Pa·s。
Embodiment 4
Equipped with blender, thermometer, condenser, low molecule receiver 5L stainless steel cauldrons in, load 2.0kg sulphur
For diethylene glycol (DEG), 0.71kg ethoxy -2- hydroxypropyl sulphides, 100g trimethylolpropanes, 22.0g p-methyl benzenesulfonic acid, 170 are warming up to
DEG C, after 170 ± 2 DEG C of reaction 7h of controlling reaction temperature, at this temperature, below overbottom pressure 2.66kPa is controlled, carry out vacuum reaction
2.5h, then removes unreacted small-molecule substance by the reaction product ethanol extraction of polycondensation reaction and obtains crude product, crude product is 140
DEG C, below overbottom pressure 2.66kPa carries out vacuum reaction 4h, obtains sulfur-containing polymer polyalcohol.Hydroxyl value 82.6mg KOH/g, viscosity
33.4Pa·s。
Embodiment 5
Equipped with blender, thermometer, condenser, low molecule receiver 5L stainless steel cauldrons in, load 2.0kg sulphur
For diethylene glycol (DEG), 0.71kg ethoxy -2- hydroxypropyl sulphides, 68.6g trimethylolpropanes, 40.0g p-methyl benzenesulfonic acid, 22.0g pairs
Toluenesulfonic acid, is warming up to 170 DEG C, after 170 ± 2 DEG C of controlling reaction temperature reacts 5h, at this temperature, control overbottom pressure 2.66kPa
Hereinafter, vacuum reaction 2.5h is carried out, unreacted small-molecule substance then is removed into the reaction product ethanol extraction of polycondensation reaction
Crude product is obtained, for crude product at 140 DEG C, below overbottom pressure 2.66kPa carries out vacuum reaction 4h, obtains sulfur-containing polymer polyalcohol.Hydroxyl value
110.2mg KOH/g, viscosity 20.2Pas.
Claims (10)
1. a kind of synthetic method of sulfur-containing polymer polyalcohol, it is characterised in that comprise the following steps：
Thiodiglycol, ethoxy -2- hydroxypropyl sulphides, trimethylolpropane are used as raw material, according to a certain ratio, in catalyst
Effect is lower carry out dehydrating polycondensation reaction after, vacuumize reaction at this temperature, it is small that reaction product through solvent extraction removes unreacted
After molecular substance, at 120~160 DEG C, below overbottom pressure 2.66kPa carries out 2~5h of vacuum reaction, and it is polynary to obtain sulfur-containing polymer
Alcohol.
2. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 1, it is characterised in that Thiodiglycol, hydroxyl second
Base -2- hydroxypropyl sulphides, the molar ratio of trimethylolpropane are 1 ﹕, 0.25~0.45 ﹕ 0.025~0.045.
3. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 2, it is characterised in that Thiodiglycol, hydroxyl second
Base -2- hydroxypropyl sulphides, the molar ratio of trimethylolpropane are 1 ﹕, 0.32 ﹕ 0.030.
4. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 1, it is characterised in that the catalyst is to first
Benzene sulfonic acid, dosage are 0.5~2.0% mass parts of Thiodiglycol dosage.
5. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 4, it is characterised in that the dosage of p-methyl benzenesulfonic acid
For 1.1% mass parts of Thiodiglycol dosage.
6. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 1, it is characterised in that the dehydrating polycondensation is anti-
It is 160~190 DEG C to answer temperature, and the reaction time is 5~8h.
7. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 6, it is characterised in that the dehydrating polycondensation is anti-
It is 170 DEG C to answer temperature, reaction time 7h.
8. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 1, it is characterised in that described to vacuumize reaction
2.5h。
9. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 8, it is characterised in that described to vacuumize reaction 2
~4h, below overbottom pressure 2.66kPa.
10. the synthetic method of sulfur-containing polymer polyalcohol as claimed in claim 1, it is characterised in that the solvent is ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711192792.7A CN107936217A (en) | 2017-11-24 | 2017-11-24 | A kind of synthetic method of sulfur-containing polymer polyalcohol |
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| CN201711192792.7A CN107936217A (en) | 2017-11-24 | 2017-11-24 | A kind of synthetic method of sulfur-containing polymer polyalcohol |
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| CN107936217A true CN107936217A (en) | 2018-04-20 |
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| CN201711192792.7A Pending CN107936217A (en) | 2017-11-24 | 2017-11-24 | A kind of synthetic method of sulfur-containing polymer polyalcohol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430325A (en) * | 2020-11-17 | 2021-03-02 | 锦西化工研究院有限公司 | Synthesis method of inertia end group polythioether polymer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2582605A (en) * | 1947-08-19 | 1952-01-15 | Socony Vacuum Oil Co Inc | Condensation of beta-hydroxyethyl sulfides with compounds containing hydroxyl groups |
| GB859027A (en) * | 1957-08-30 | 1961-01-18 | Bayer Ag | Heat-sensitising agents |
| US4284761A (en) * | 1980-07-23 | 1981-08-18 | American Cyanamid Co. | Thiodiethanol-based polyurethane elastomers having improved dynamic properties and method for production thereof |
| US4349656A (en) * | 1980-07-23 | 1982-09-14 | American Cyanamid Company | Thiodiethanol based polyurethane elastomers having improved dynamic properties and method for production thereof |
| US4366307A (en) * | 1980-12-04 | 1982-12-28 | Products Research & Chemical Corp. | Liquid polythioethers |
| CN104968645A (en) * | 2013-01-29 | 2015-10-07 | 巴斯夫欧洲公司 | Polysulfide polyols, their production and use in the synthesis of polyurethanes |
-
2017
- 2017-11-24 CN CN201711192792.7A patent/CN107936217A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2582605A (en) * | 1947-08-19 | 1952-01-15 | Socony Vacuum Oil Co Inc | Condensation of beta-hydroxyethyl sulfides with compounds containing hydroxyl groups |
| GB859027A (en) * | 1957-08-30 | 1961-01-18 | Bayer Ag | Heat-sensitising agents |
| US4284761A (en) * | 1980-07-23 | 1981-08-18 | American Cyanamid Co. | Thiodiethanol-based polyurethane elastomers having improved dynamic properties and method for production thereof |
| US4349656A (en) * | 1980-07-23 | 1982-09-14 | American Cyanamid Company | Thiodiethanol based polyurethane elastomers having improved dynamic properties and method for production thereof |
| US4366307A (en) * | 1980-12-04 | 1982-12-28 | Products Research & Chemical Corp. | Liquid polythioethers |
| CN104968645A (en) * | 2013-01-29 | 2015-10-07 | 巴斯夫欧洲公司 | Polysulfide polyols, their production and use in the synthesis of polyurethanes |
Non-Patent Citations (2)
| Title |
|---|
| 许长清: "《合成树脂及塑料手册》", 30 November 1991, 化学工业出版社 * |
| 赵德明: "《有机合成工艺》", 30 June 2012, 浙江大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430325A (en) * | 2020-11-17 | 2021-03-02 | 锦西化工研究院有限公司 | Synthesis method of inertia end group polythioether polymer |
| CN112430325B (en) * | 2020-11-17 | 2023-11-03 | 锦西化工研究院有限公司 | Synthesis method of inert end group polythioether polymer |
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