CN112280030A - Polyether polyol, preparation method and application thereof - Google Patents
Polyether polyol, preparation method and application 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine 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
- C08G18/28—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
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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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
Abstract
The invention discloses polyether polyol, a preparation method and application thereof, wherein the polyether polyol is mainly prepared by condensation of itaconic anhydride and polyamine to form polyimide and addition of double bonds on the itaconic anhydride and mercapto alcohol or alcohol monomers containing the double bonds. The polyether polyol can be used for preparing a polyurethane material, and the polyurethane material is used for manufacturing a plastic track. The polyurethane prepared from the modified polyether polyol has excellent high temperature resistance, good mechanical strength, lower thermal expansion coefficient and excellent flame retardant property, and is suitable for being applied to places which need high temperature resistance and have high requirements on mechanical properties.
Description
Technical Field
The invention belongs to the field of polymer polyol, and particularly relates to polyether polyol, and a preparation method and application thereof.
Background
Polyether polyol (polyether for short) is prepared by the polyaddition reaction of an initiator (compound containing active hydrogen groups) and Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO) and the like in the presence of a catalyst. Polyether polyol series products are mainly used for preparing rigid polyurethane foam plastics and are widely applied to the fields of refrigerators, freezers, refrigerated trucks, heat insulation boards, pipeline heat insulation and the like.
However, for some fields with high temperature resistance, it is difficult to achieve the high temperature resistance after curing the common polyether polyol and isocyanate, such as in the field of plastic track. The plastic track is generally exposed to outdoor conditions, and the outdoor ground surface temperature can reach 50-60 ℃ in high-temperature seasons in summer, so that the plastic track can emit strong rubber smell at high temperature, serious health hidden dangers are caused to people in motion, and the plastic track is required to have good high-temperature resistance and the volatilization of toxic and harmful components is reduced. In addition, for some polyurethane materials which are not resistant to high temperature, the adhesive property of the materials can be rapidly reduced under the condition of high temperature, so that the materials and the base materials fall off, and the use of equipment is influenced.
Polyimide is a high molecular material with high modulus, high strength, low hydrolysis and other excellent physical and mechanical properties and chemical stability. Polyimide has ultrahigh heat resistance (more than 400 ℃), not only has good heat resistance, but also has a wide temperature use range (-200 ℃ to 300 ℃) and can be selected by people, so the polyimide is called as one of the most promising materials in the 21 st century.
For the high temperature resistant polyurethane composite material, the isocyanate component is generally subjected to graft modification, so that the material obtains certain high temperature resistance, and the polyether polyol component is slightly modified. Patent CN201310315037.9 discloses a dripping-resistant and high-temperature-resistant polyimide polyurethane and a preparation method thereof, wherein polyimide is also introduced into a polyurethane material, but in the process of preparing the polyurethane material by the method disclosed by the patent, the reactivity of isocyanate and anhydride needs to be further verified, and the reaction yield is not mentioned.
Disclosure of Invention
The polyether polyol contains a polyimide structure, and can be used for preparing polyurethane, and the prepared polyurethane has excellent heat resistance and mechanical properties.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polyether polyol of the formula:
wherein R is selected from any one of an alkyl structure, an alicyclic structure or an aromatic structure, and R' is a mercapto-containing alcohol structure with or without a branched chain, or a double bond-containing alcohol structure with or without a branched chain.
Further, the polyether polyol is prepared by adopting the reaction comprising the following components:
a. a poly-primary amine,
b. itaconic anhydride or an isomerisation product thereof,
c. a component of a mercapto group-containing alcohol structure or a double bond-containing alcohol structure,
d. catalyst and process for preparing same
e. An initiator;
the mol ratio of the amino group in the component a to the components b and c is 1: 0.8-1.2: 0.8 to 1.2, preferably 1: 0.95-1.05: 0.95 to 1.05.
Further, the primary polyamine of component a has a structure containing two or more primary amines, and is preferably a combination of one or more of aromatic primary polyamine, alicyclic primary polyamine, and aliphatic primary polyamine, such as m-xylylenediamine, 4 '-diaminodicyclohexylmethane, isophoronediamine, ethylenediamine, hexamethylenediamine, and further preferably 4,4' -diaminodicyclohexylmethane and isophoronediamine in terms of waals chemistry.
Further, the thiol-group-containing alcohol structure of the component c includes, but is not limited to, 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, 6-mercaptohex-1-ol, 3-mercapto-1-hexanol, 4-mercaptobenzyl alcohol, 3-mercapto-2-butanol, 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol, 3-mercapto-2-methylpentanol, 3-mercapto-3-methyl-1-butanol, 4-mercapto-1-butanol, 1-mercapto-2-propanol, 2-mercaptoethoxyethanol, 11-mercapto-1-undecanol;
further, the double bond-containing alcohol structure includes, but is not limited to, one or a combination of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, allyl alcohol, methallyl alcohol, allyl polyethylene glycol and methallyl alcohol polyoxyethylene ether.
Further, the initiator is persulfate, peroxide, organic hydroperoxide, organic peracid or azo compound; preferably ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, dibenzoyl peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis (2-amidinopropane) dihydrochloride or 2, 2' -azobis (2-methyl-butyronitrile).
Further, the catalyst is a tertiary amine catalyst, preferably triethylamine.
Further, the reaction also comprises a component f dehydrating agent, wherein the dehydrating agent is an anhydride dehydrating agent, and is preferably acetic anhydride.
The invention also provides a preparation method of the polyether polyol, which comprises the following steps:
(1) adding a certain amount of the component a and the component b into a dry reaction container, then adding a solvent, stirring for 4-6h at room temperature under the protection of nitrogen, then adding a component d catalyst, continuously stirring for 3-4h at room temperature, continuously adding a component f dehydrating agent, stirring for 3-4h, dehydrating and cyclizing to obtain an imide product;
(2) dissolving an imide product in a flux, adding a component c containing a mercapto-containing component with an alcohol structure or a double-bond component with an alcohol structure, adding a small amount of a component e initiator, and carrying out mercapto-alkene addition reaction or double-bond free radical addition reaction under the illumination of 350-400 nm;
(3) adding the obtained addition reaction product into an ether solvent, preferably petroleum ether, and filtering to obtain polyether polyol.
Further, the addition amount of the component d is 0.5 to 2 percent of the total weight of the component a, the component b and the solvent added in the step (1), and preferably 0.8 to 1 percent; the addition amount of the component e is 0.2-3 percent of the total weight of the added imide product and the component c, preferably 0.4-1 percent, and the addition amount of the dehydrating agent is 0.5-2 percent of the total weight of the component a, the component b and the solvent added in the step (1), preferably 0.8-1 percent; wherein the addition amount of the solvent in the step (1) is 8-30 times of the total weight of the component a and the component b, and preferably 10-25 times.
Preferably, the solvent in the step (1) and the solvent in the step (2) are a tetrahydrofuran/methanol mixed solution, N-dimethylacetamide, dimethylformamide or other solvents.
The invention also provides application of the polyether polyol or the polyether polyol prepared by the method, which is used for preparing polyurethane, wherein the polyurethane can be used for plastic runways and other fields needing high temperature resistance.
The invention has the beneficial effects that:
(1) in the invention, a polyimide structure is introduced into the polyol, and the generated polyol is used for preparing the polyurethane material, so that the polyurethane material has excellent high-temperature resistance and is suitable for being applied to places needing high-temperature resistance. The polyether polyol can be used as a curing agent of isocyanate alone, and can also be used as a chain extender to be matched with other polyols for use.
(2) According to the preparation method of the polyol, the polyamine with different structures can be selected to prepare the polyol with different hydroxyl numbers according to the actual application requirements, the polyol with multiple structures can be flexibly prepared, the crosslinking density of a cured product can be improved due to more hydroxyl numbers, the heat resistance and the mechanical strength of the cured product are further improved, and the prepared polyol has a lower thermal expansion coefficient and excellent flame retardant property.
(3) According to the invention, alcohol monomers with different systems and different hydroxyl numbers can be selected to carry out grafting reaction according to actual application requirements, so that polyhydric alcohols with different molecular chain lengths can be prepared, primary alcohols, secondary alcohols and the like with different structures can also be prepared, and different application requirements can be met.
(4) The modified polyol prepared by the method can be independently cured with isocyanate, can also be used as a chain extender to be matched with other polyols for use, and has a wide application range.
Drawings
FIG. 1 is an IR chart of the polyether polyol prepared in example 6.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The names, abbreviations and sources of the main chemicals used in the examples of the present invention are shown in the following table. The reagents used are all chemically pure unless otherwise indicated.
TABLE 1
| Chemical name | Source |
| Itaconic anhydride | Aladdin |
| M-xylylenediamine (MXDA) | Aladdin |
| 2-mercaptoethanol | Aladdin |
| Polymeric diphenylmethane diisocyanate (PM200) | Wanhua chemistry |
| 4,4' -Diaminodicyclohexylmethane (HMDA) | Wanhua chemistry |
| Polyetheramine wanamine8100 | Wanhua chemistry |
| Polyether amine T403 | Henscman chemistry |
| Hydroxyethyl acrylate (HEMA) | Wanhua chemistry |
| Polyether polyol DL2000 | Wanhua chemistry |
Example 1
(1) 5.61g of itaconic anhydride and 3.40g of m-xylylenediamine were added to a dry three-necked flask, 200ml of N, N-Dimethylacetamide (DMAC) was added, and the mixture was stirred at room temperature for 6 hours under nitrogen protection, 2g of triethylamine was added, stirring at room temperature was continued for 4 hours, and 2g of acetic anhydride was added, and stirring was continued for 4 hours. After the reaction is finished, pouring the reaction system into ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 8.1g of the crude imide product was dissolved in DMAC, 4.0g of 2-mercaptoethanol and 0.06g of benzoyl peroxide as an initiator were added, and mercapto-ene addition reaction was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 2
(1) 5.61g of itaconic anhydride and 5.25g of 4,4' -diaminodicyclohexylmethane are added to a dry three-necked flask, 200ml of N, N-Dimethylacetamide (DMAC) is added and stirred at room temperature for 6h under nitrogen protection, 2g of triethylamine is added and stirring at room temperature is continued for 4h, and 2g of acetic anhydride is added and stirring is continued for 4 h. After the reaction is finished, pouring the reaction system into ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 10g of the crude imide product was dissolved in DMAC, 4.0g of 2-mercaptoethanol and 0.07g of benzoyl peroxide as an initiator were added, and mercapto-ene addition reaction was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 3
(1) 5.61g of itaconic anhydride and 5.75g of polyetheramine wanamine8100 are added to a dry three-neck flask, then 200ml of N, N-Dimethylacetamide (DMAC) is added, stirring is carried out at room temperature for 6h under the protection of nitrogen, then 2g of triethylamine is added, stirring is carried out at room temperature for 4h, and 2g of acetic anhydride is added, and stirring is carried out for 4 h. After the reaction is finished, pouring the reaction system into hot ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 10.5g of the crude imide product was dissolved in DMAC, 4.0g of 2-mercaptoethanol and 0.07g of the photoinitiator benzoyl peroxide were added and the mercapto-ene addition reaction was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 4
(1) 8.42g of itaconic anhydride and 10.0g of polyetheramine T403 are added to a dry three-neck flask, then 200ml of N, N-Dimethylacetamide (DMAC) are added and stirred at room temperature for 6h under nitrogen protection, then 2g of triethylamine are added and stirring is continued at room temperature for 4h, and 2g of acetic anhydride is added and stirring is continued for 4 h. After the reaction is finished, pouring the reaction system into hot ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 15.7g of the crude imide product were dissolved in DMAC, 5.9g of 2-mercaptoethanol and 0.108g of the initiator benzoyl peroxide were added and the mercapto-ene addition reaction was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 5
(1) 5.61g of itaconic anhydride and 3.40g of m-xylylenediamine were added to a dry three-necked flask, 200ml of N, N-Dimethylacetamide (DMAC) was added, and the mixture was stirred at room temperature for 6 hours under nitrogen protection, 2g of triethylamine was added, stirring at room temperature was continued for 4 hours, and 2g of acetic anhydride was added, and stirring was continued for 4 hours. After the reaction is finished, pouring the reaction system into hot ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 8.1g of the crude imide product was dissolved in DMAC, 5.8g of hydroxyethyl acrylate and 0.07g of the photoinitiator benzoyl peroxide were added, and double bond addition was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 6
(1) 5.61g of itaconic anhydride and 5.25g of 4,4' -diaminodicyclohexylmethane are added to a dry three-necked flask, 200ml of N, N-Dimethylacetamide (DMAC) is added and stirred at room temperature for 6h under nitrogen protection, 2g of triethylamine is added and stirring at room temperature is continued for 4h, and 2g of acetic anhydride is added and stirring is continued for 4 h. After the reaction is finished, pouring the reaction system into hot ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 10g of the crude imide product was dissolved in DMAC, 5.8g of hydroxyethyl acrylate and 0.08g of benzoyl peroxide as initiator were added, and double bond addition was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Example 7
(1) 8.42g of itaconic anhydride and 10g of polyetheramine T403 are added to a dry three-neck flask, then 200ml of N, N-Dimethylacetamide (DMAC) are added and stirred at room temperature for 6h under nitrogen protection, then 2g of triethylamine are added and stirring is continued at room temperature for 4h, and 2g of acetic anhydride is added and stirring is continued for 4 h. After the reaction is finished, pouring the reaction system into hot ethanol, separating out yellow solid, and filtering to obtain an imide crude product; (2) 15.7g of the crude imide product were dissolved in DMAC, 8.7g of hydroxyethyl acrylate and 0.122g of benzoyl peroxide as initiator were added, and double bond addition was carried out under 365nm light. Pouring the obtained addition reaction product into petroleum ether, and filtering to obtain a viscous product polyether polyol; (3) and (3) reacting the polyether polyol obtained in the step (2) with PM200 to obtain the high-temperature-resistant polyurethane cured product.
Comparative example 1:
polyether polyol DL2000 and polymeric diphenylmethane diisocyanate 200(PM200) are mixed and stirred uniformly, and after full reaction, a polyurethane condensate is obtained.
To further illustrate the high temperature resistance of the polyether polyol of the present invention, DSC thermal decomposition test was performed on the polyurethane sample blocks obtained in examples 1 to 7 and the polyurethane sample block obtained in comparative example 1, according to ISO 11358 Plastic-thermal weight loss method, and the test results are shown in Table 2.
TABLE 2
| Numbering | Bulk decomposition temperature (. degree. C.) |
| Example 1 | 510.2 |
| Example 2 | 483.5 |
| Example 3 | 421.6 |
| Example 4 | 450.3 |
| Example 5 | 516.3 |
| Example 6 | 485.2 |
| Example 7 | 453.5 |
| Comparative example 1 | 387.1 |
From the tested DSC thermal decomposition temperature, the thermal decomposition temperature of the polyurethane material prepared by using the modified polyether polyol in the invention is obviously higher than that of the polyurethane material prepared by using the conventional polyether polyol, so that the modified polyol and isocyanate in the invention have obvious high temperature resistance after curing.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A polyether polyol characterized by the structural formula:
wherein R is selected from any one of an alkyl structure, an alicyclic structure or an aromatic structure, and R' is a mercapto-containing alcohol structure with or without a branched chain, or a double bond-containing alcohol structure with or without a branched chain.
2. Polyether polyol according to claim 1, characterized in that it is prepared by a reaction comprising:
a. a poly-primary amine,
b. itaconic anhydride or an isomerisation product thereof,
c. a component of a mercapto group-containing alcohol structure or a double bond-containing alcohol structure,
d. a catalyst,
e. an initiator;
the mol ratio of the amino group in the component a to the components b and c is 1: 0.8-1.2: 0.8 to 1.2, preferably 1: 0.95-1.05: 0.95 to 1.05.
3. Polyether polyol according to claim 2, wherein the primary polyamine of component a comprises more than two primary amine structures, preferably a combination of one or more of aromatic primary polyamines, cycloaliphatic primary polyamines, aliphatic primary polyamines, such as m-xylylenediamine, 4 '-diaminodicyclohexylmethane, isophoronediamine, ethylenediamine, hexamethylenediamine, further preferably 4,4' -diaminodicyclohexylmethane and isophoronediamine in the Wanhua chemistry.
4. Polyether polyol according to claim 2 or 3, the alcohol structure containing the sulfhydryl of the component c is one or a composition of more than two of 2-mercaptoethanol, 3-sulfhydryl-1, 2-propylene glycol, 6-mercaptohexan-1-ol, 3-sulfhydryl-1-hexanol, 4-mercaptobenzyl alcohol, 3-sulfhydryl-2-butanol, 3- ((2-sulfhydryl-1-methylpropyl) thio) -2-butanol, 3-sulfhydryl-2-methylpentanol, 3-sulfhydryl-3-methyl-1-butanol, 4-sulfhydryl-1-butanol, 1-sulfhydryl-2-propanol, 2-mercaptoethoxyethanol and 11-sulfhydryl-1-undecanol;
the double-bond-containing alcohol structure is one or a composition of more than two of hydroxyethyl acrylate, hydroxypropyl acrylate, allyl alcohol, methallyl alcohol, allyl polyethylene glycol and methallyl alcohol polyoxyethylene ether.
5. Polyether polyol according to any of claims 2 to 4 wherein the initiator is a persulfate, a peroxide, an organic hydroperoxide, an organic peracid or an azo compound; preferably ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, dibenzoyl peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis (2-amidinopropane) dihydrochloride or 2, 2' -azobis (2-methyl-butyronitrile).
6. Polyether polyol according to any of claims 2 to 5, wherein the catalyst is a tertiary amine based catalyst, preferably triethylamine.
7. Polyether polyol according to any of claims 2 to 6, wherein the reaction further comprises a component f a dehydrating agent, which is an anhydride-based dehydrating agent, preferably acetic anhydride.
8. A process for the preparation of a polyether polyol according to any of claims 2 to 7, comprising the steps of:
(1) adding the component a and the component b into a dry reaction container, then adding a solvent, stirring for 4-6h at room temperature under the protection of nitrogen, then adding a component d catalyst, continuously stirring for 3-4h, continuously adding a component f dehydrating agent, stirring for 3-4h, dehydrating and cyclizing to obtain an imide product;
(2) dissolving an imide product in a solvent, adding a component c containing a mercapto-containing alcohol structure or a double-bond-containing alcohol structure, adding a small amount of a component e initiator, and performing mercapto-alkene addition or double-bond free radical addition reaction under the illumination of 350-400 nm;
(3) adding the obtained addition reaction product into an ether solvent, preferably petroleum ether, and filtering to obtain polyether polyol.
9. The preparation method according to claim 8, wherein the component d is added in an amount of 0.5-2%, preferably 0.8-1% of the total weight of the components a, b and the solvent added in step (1); the addition amount of the component e is 0.2-3 percent of the total weight of the added imide product and the component c, preferably 0.4-1 percent, and the addition amount of the dehydrating agent is 0.5-2 percent of the total weight of the component a, the component b and the solvent added in the step (1), preferably 0.8-1 percent; wherein the addition amount of the solvent in the step (1) is 8-30 times of the total weight of the component a and the component b, and preferably 10-25 times.
10. The method according to claim 8 or 9, wherein the solvent in the step (1) and the step (2) is a tetrahydrofuran/methanol mixed solution, N-dimethylacetamide, or dimethylformamide, respectively.
11. Use of a polyether polyol according to any one of claims 1 to 7 or prepared by a process according to any one of claims 8 to 10 for the preparation of a polyurethane.
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| CN114411429A (en) * | 2021-12-15 | 2022-04-29 | 安徽大学 | Electron beam cured waterproof moisture-permeable waterborne polyurethane fabric coating adhesive and preparation method thereof |
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| CN101784540A (en) * | 2007-07-26 | 2010-07-21 | 汉高股份两合公司 | alcohols containing imide moieties and reactive oligomers prepared therefrom |
| US20120225101A1 (en) * | 2011-03-02 | 2012-09-06 | Kao Weiyuan J | Multifunctional in situ polymerized network via thiol-ene and thiol-maleimide chemistry |
| WO2019105935A1 (en) * | 2017-11-29 | 2019-06-06 | Covestro Deutschland Ag | Imide-containing polyester |
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| CN101784540A (en) * | 2007-07-26 | 2010-07-21 | 汉高股份两合公司 | alcohols containing imide moieties and reactive oligomers prepared therefrom |
| US20120225101A1 (en) * | 2011-03-02 | 2012-09-06 | Kao Weiyuan J | Multifunctional in situ polymerized network via thiol-ene and thiol-maleimide chemistry |
| WO2019105935A1 (en) * | 2017-11-29 | 2019-06-06 | Covestro Deutschland Ag | Imide-containing polyester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411429A (en) * | 2021-12-15 | 2022-04-29 | 安徽大学 | Electron beam cured waterproof moisture-permeable waterborne polyurethane fabric coating adhesive and preparation method thereof |
| CN114411429B (en) * | 2021-12-15 | 2023-06-20 | 安徽大学 | Electron beam curing waterproof moisture-permeable aqueous polyurethane fabric coating adhesive and preparation method thereof |
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