CN112280029A - Preparation method of alkynyl polyether - Google Patents
Preparation method of alkynyl polyether Download PDFInfo
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- 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
- C08G65/04—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 only
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Abstract
The invention belongs to the field of chemical industry, and provides a preparation method of alkynyl polyether. Compared with the prior art, the method is cheaper, simpler in formula, more convenient to operate, green, safe, efficient and environment-friendly, and is suitable for industrial production. Because the acetylene bond has higher activity than double bonds, compared with allyl polyether, the alkynyl polyether has higher activity, the addition reaction condition of the alkynyl polyether and the organic silicon hydride is milder, and the equipment requirement is lower, so the alkynyl polyether synthesized by the method has wider application prospect.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to alkynyl polyether, in particular to a preparation method of alkynyl polyether.
Background
Conventional unsaturated polyethers are those obtained by reacting an alcohol having an unsaturated double bond as an initiator with an epoxy monomer such as Ethylene Oxide (EO) and Propylene Oxide (PO). The alcohol having an unsaturated double bond includes allyl alcohol, methallyl alcohol and the like. The unsaturated polyether is mainly used for preparing the polyether modified organic silicon surfactant by reacting unsaturated double bonds with hydrogen-containing silicone oil.
Polyether structures used in the hydrosilation reaction are different, and polyether modified organic silicon with different molecular structures is obtained. The most demanded in the market at present are allyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene random polyether and methallyl alcohol polyoxyethylene polyoxypropylene random polyether. The hydrosilylation reaction is carried out under severe conditions due to the use of a platinum catalyst. From the hydrosilylation reaction mechanism, the quality of the highly reactive polyethers, especially unsaturated polyethers, affects the quality of the polyether-modified silicones. Unsaturated polyethers with high reactivity require high double bond content, low content of by-products such as bishydroxy polyether, and narrow molecular weight distribution.
CN200910198310.8 discloses a preparation method of allyl polyoxyethylene ether, which takes allyl alcohol and ethylene oxide as raw materials to prepare a product through two-step polymerization. The method comprises the following steps: carrying out a first-step polymerization reaction on allyl alcohol and ethylene oxide in the presence of a catalyst, wherein the reaction time is 3-6 hr, and the catalyst is sodium allyl alcohol or potassium allyl alcohol; vacuumizing the system to remove unreacted ethylene oxide and low molecular weight substances; replenishing the catalyst, and adding ethylene oxide to perform a second-step polymerization reaction for 2-6 hr, wherein the catalyst is sodium allyl alcohol or potassium allyl alcohol; acid was added to the product to neutralize the catalyst, which was cooled and filtered to remove solids.
CN201510473015.4 discloses a production method of allyl polyether with high double bond content, belonging to the technical field of polyether compound synthesis in organic chemistry. Mixing propylene alcohol and an epoxy compound for reaction under the catalysis of a sodium propylene alcohol solution at 110-140 ℃ in an oxygen-free environment, and aging and cooling after the reaction is finished to obtain a crude propyl polyether product; and mixing the allyl polyether crude product with water, neutralizing, filtering, and taking a liquid phase to obtain the allyl polyether. The molecular weight of the allyl polyether prepared by the method is 200-8000, the double bond content is more than or equal to 98%, and the molecular weight distribution coefficient is less than or equal to 1.05. The method uses metal sodium as a catalyst, the metal sodium is flammable and explosive, and reacts with allyl alcohol to generate hydrogen, so that the industrial production is difficult to realize.
CN102898639A discloses a method for synthesizing methallyl alcohol polyoxyethylene ether, which comprises the steps of firstly using sodium, potassium or sodium hydride to react with methallyl alcohol at 20-60 ℃ to prepare a catalyst 1, adding the catalyst 1 into methallyl alcohol to react with ethylene oxide to prepare an oligomer of methallyl alcohol polyoxyethylene ether, then using the oligomer of sodium, potassium or sodium hydride and methallyl alcohol polyoxyethylene ether to react at 30-60 ℃ to prepare a catalyst 2, adding the catalyst 2 into the oligomer of methallyl alcohol polyoxyethylene ether to react with ethylene oxide to prepare the methallyl alcohol polyoxyethylene ether. The method needs 2 times of catalyst preparation, has complex procedures and is difficult to realize industrialization.
In the synthesis of the polyether, sodium hydroxide and potassium hydroxide are mostly adopted as catalysts, the sodium hydroxide, the potassium hydroxide and alcoholic hydroxyl react to produce water, and the water further reacts with ethylene oxide and propylene oxide to generate a byproduct of dihydroxy polyether; when sodium methoxide and potassium methoxide are used as catalysts, the sodium methoxide and the potassium methoxide react with alcoholic hydroxyl to generate methanol, the methanol further reacts with ethylene oxide and propylene oxide to generate a byproduct, namely methyl alkoxylate, and in the process, although the methanol is easy to remove, the sodium methoxide and the potassium methoxide are highly flammable chemicals, and the generated methanol is a toxic liquid and pollutes the environment; the metal sodium or potassium is used as a catalyst, although the generation of byproducts can be avoided, the metal sodium or potassium is inflammable, and hydrogen generated with unsaturated alcohol is inflammable, so that the industrial production is difficult to realize.
Based on the above, the invention provides a method for synthesizing alkynyl polyether by taking phenyl alkyne as an initiator and copper salt or a complex thereof as a catalyst. Because the acetylene bond has higher activity than a double bond, compared with allyl polyether, the alkynyl polyether has higher activity, and the addition reaction condition of the alkynyl polyether and the organosilicon hydride is milder and has lower equipment requirement.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing alkynyl polyether by taking phenylalkyne as an initiator and copper salt or a complex thereof as a catalyst.
The invention provides a preparation method of alkynyl polyether, which takes phenylalkyne with the following structural formulas (1), (2) and (3) as a raw material, and reacts with an epoxy compound under the action of a copper catalyst and alkali to generate alkynyl polyether with the corresponding structural formulas (4), (5) and (6):
wherein:
represents a benzene ring containing 0 to 5 identical or different substituents selected from linear or branched alkyl, aryl, halogen, groups containing oxygen, nitrogen or sulfur atoms;
the structural formula (1) shows that an alkynyl is connected on a benzene ring containing 0-5 same or different substituents;
the structural formula (2) shows that two alkynyl groups are connected on a benzene ring containing 0-5 same or different substituent groups, and the relative position of the alkynyl groups can be ortho-position, meta-position or para-position;
the structural formula (3) shows that three alkynyl groups are connected on a benzene ring containing 0-5 same or different substituent groups, and the relative position of the alkynyl groups can be any position;
l represents a polyether chain with an initiating terminal being alkynyl and containing a plurality of ethylene oxide and propylene oxide units, m is the number of ethylene oxide units, n is the number of propylene oxide units, 200 is more than or equal to m and more than or equal to 0, and 200 is more than or equal to n and more than or equal to 0;
the structural formulas (4), (5) and (6) represent polyether chains L which are respectively connected with one, two and three alkynyl starting ends on benzene rings containing 0-5 same or different substituents.
Further, the epoxy compound is selected from a mixture of ethylene oxide and propylene oxide.
Further, the total weight ratio of the phenylalkyne to the epoxy compound is 1: 5 to 100.
Further, the copper catalyst is selected from copper salts, and the weight ratio of the copper catalyst to the phenylalkyne is 1: 10 to 100.
Further, the copper catalyst is selected from CuI, CuCl, CuBr and Cu2O、Cu(acac)2CuCl2、CuBr2、CuI2、Cu(OAc)2、Cu(OTf)2、Cu(ClO4)2Or CuSO4Any one of them.
Further, the base is selected from organic or inorganic bases, and the organic base is triethylamine, 1, 8-diazabicycloundece-7-ene and diisopropylethylamineThe inorganic base is KOH or K2CO3、NaOH、Na2CO3、Cs2CO3、CsOH、K3PO4、K2HPO4、Na3PO4Or Na2HPO4In a weight ratio of base to phenylalkyne of 1: 10 to 100.
Further, weighing each reaction substance according to the weight fraction, adding phenyl alkyne, alkali and a copper catalyst into a reaction container at room temperature, introducing an epoxy compound, heating to 50-80 ℃ for polymerization, and reacting for 3-6 hours to obtain the alkynyl polyether.
The reaction principle and the beneficial effects of the invention are as follows:
the invention realizes the synthesis of alkynyl polyether by utilizing the nucleophilic ring-opening reaction of alkynyl on epoxy compound under the action of copper catalyst and alkali.
Compared with the prior art, the invention has the advantages of positive and obvious technical effect. The method is cheaper, the formula is simpler, the operation is more convenient, and meanwhile, the method is green, safe, efficient and environment-friendly and is suitable for industrial production. The alkynyl polyether has higher activity than double bond, has milder addition reaction condition with organosilicon hydride and lower equipment requirement compared with allyl polyether, and the reaction temperature can be as low as 50 ℃ as proved by the embodiment of the invention, so the alkynyl polyether synthesized by the method has wider application prospect.
Detailed Description
Example 1
Synthesizing alkynyl polyether by taking phenylacetylene as a raw material:
under nitrogen atmosphere, adding 10 parts by weight of phenylacetylene, 1 part by weight of triethylamine and 0.5 part by weight of CuI into a reaction kettle, stirring for 10 minutes at room temperature, adding 500 parts by weight of ethylene oxide and 450 parts by weight of propylene oxide, heating to 50 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 3 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 2
Synthesizing alkynyl polyether by taking p-methyl phenylacetylene as a raw material:
under a nitrogen atmosphere, 11 parts by weight of p-methylphenylacetylene, 1 part by weight of DBU (1, 8-diazabicycloundecen-7-ene) and 0.6 part by weight of Cu (OAc)2Stirring for 10 minutes at room temperature, adding 600 parts by weight of ethylene oxide and 300 parts by weight of propylene oxide, heating to 60 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 3 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 3
Synthesizing alkynyl polyether by taking 2-ethynyl-1, 3, 5-trimethylbenzene as a raw material:
under nitrogen atmosphere, 13 weight parts of 2-ethynyl-1, 3, 5-trimethylbenzene and 1 weight part of Cs are added into a reaction kettle2CO3And 0.7 parts by weight of Cu (OTf)2Stirring for 10 minutes at room temperature, adding 600 parts by weight of ethylene oxide and 400 parts by weight of propylene oxide, heating to 80 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 4 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 4
Taking 1, 2-diacetylene benzene as a raw material to synthesize alkynyl polyether:
under nitrogen atmosphere in13 parts by weight of 1, 2-diethynylbenzene, 1 part by weight of diisopropylethylamine and 0.8 part by weight of Cu (ClO) were charged in a reaction vessel4)2Stirring for 10 minutes at room temperature, adding 500 parts by weight of ethylene oxide and 400 parts by weight of propylene oxide, heating to 70 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 4 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 5
Taking 1, 3-diacetylene benzene as a raw material to synthesize alkynyl polyether:
under nitrogen atmosphere, adding 12 parts by weight of 1, 3-diethynylbenzene, 1 part by weight of diisopropylethylamine and 0.7 part by weight of CuBr into a reaction kettle, stirring for 10 minutes at room temperature, adding 500 parts by weight of ethylene oxide and 400 parts by weight of propylene oxide, heating to 70 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 4 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 6
1, 4-diacetylene benzene is used as a raw material to synthesize alkynyl polyether:
under nitrogen atmosphere, 12 parts by weight of 1, 4-diethynylbenzene, 1 part by weight of DBU and 0.6 part by weight of Cu were charged in a reaction vessel2And O, stirring for 10 minutes at room temperature, adding 450 parts by weight of ethylene oxide and 400 parts by weight of propylene oxide, heating to 60 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 3 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 7
Synthesizing alkynyl polyether by using 2, 4-diacetylene-1-methoxybenzene as a raw material:
under nitrogen atmosphere, adding 12 parts by weight of 2, 4-diacetylene-1-methoxybenzene, 1 part by weight of diisopropylethylamine and 0.6 part by weight of CuCl into a reaction kettle, stirring for 10 minutes at room temperature, adding 500 parts by weight of ethylene oxide and 450 parts by weight of propylene oxide, heating to 80 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 5 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 8
Synthesizing alkynyl polyether by taking 2, 4, 6-triethynyl-1-methoxybenzene as a raw material:
under nitrogen atmosphere, adding 13 parts by weight of 2, 4, 6-triethylalkynyl-1-methoxybenzene, 1 part by weight of DBU and 0.6 part by weight of CuI into a reaction kettle, stirring for 10 minutes at room temperature, adding 400 parts by weight of ethylene oxide and 450 parts by weight of propylene oxide, heating to 80 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 6 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
Example 9
Synthesizing alkynyl polyether by taking N- (2, 4, 6-triethynyl benzene) acetamide as a raw material:
under a nitrogen atmosphere, a reaction vessel was charged with 14 parts by weight of N- (2, 4, 6-triethylynylbenzene) acetamide, 1 part by weight of diisopropylethylamine and 0.6 part by weight of Cu (OTf)2Stirring for 10 minutes at room temperature, adding 450 parts by weight of ethylene oxide and 450 parts by weight of propylene oxide, heating to 80 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 6 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and passing throughAnd filtering to obtain the product.
Example 10
Synthesizing alkynyl polyether by taking 2, 3-diacetylene naphthalene as a raw material:
under a nitrogen atmosphere, 13 parts by weight of 2, 3-diacetylnaphthalene, 1 part by weight of diisopropylethylamine and 0.7 part by weight of Cu (ClO) were added to a reaction vessel4)2Stirring for 10 minutes at room temperature, adding 500 parts by weight of ethylene oxide and 400 parts by weight of propylene oxide, heating to 70 ℃ for polymerization, controlling the reaction pressure to be 0.05-0.20 Mpa, reacting for 4 hours, cooling to room temperature, pumping into a post-treatment kettle, treating with a polyether adsorbent, and filtering to obtain the product.
The alkynyl polyether prepared by the above embodiments is tested, and the specific indexes are as follows:
the molecular weight is calculated by converting the hydroxyl value of the polyether, and the detection method of the hydroxyl value is carried out according to the national standard GB 12008.3. The degree of unsaturation is determined by the iodine value method, with reference to the national standard GB/T13892.
As can be seen from the above examples, the reaction temperature of the present invention is lower, the lowest temperature can be as low as 50 ℃, and the operation is simpler.
Claims (7)
1. A preparation method of alkynyl polyether is characterized by comprising the following steps: taking phenyl alkyne of the following structural formulas (1), (2) and (3) as a raw material, and reacting the phenyl alkyne with an epoxy compound under the action of a copper catalyst and alkali to generate alkynyl polyether of the corresponding structural formulas (4), (5) and (6):
wherein:
represents a benzene ring containing 0 to 5 identical or different substituents selected from linear or branched alkyl, aryl, halogen, groups containing oxygen, nitrogen or sulfur atoms;
the structural formula (1) shows that an alkynyl is connected on a benzene ring containing 0-5 same or different substituents;
the structural formula (2) shows that two alkynyl groups are connected on a benzene ring containing 0-5 same or different substituent groups, and the relative position of the alkynyl groups can be ortho-position, meta-position or para-position;
the structural formula (3) shows that three alkynyl groups are connected on a benzene ring containing 0-5 same or different substituent groups, and the relative position of the alkynyl groups can be any position;
l represents a polyether chain with an initiating terminal being alkynyl and containing a plurality of ethylene oxide and propylene oxide units, m is the number of ethylene oxide units, n is the number of propylene oxide units, 200 is more than or equal to m and more than or equal to 0, and 200 is more than or equal to n and more than or equal to 0;
the structural formulas (4), (5) and (6) represent polyether chains L which are respectively connected with one, two and three alkynyl starting ends on benzene rings containing 0-5 same or different substituents.
2. The method for preparing alkynyl polyether according to claim 1, wherein: the epoxy compound is selected from a mixture of ethylene oxide and propylene oxide.
3. The method for preparing alkynyl polyether according to claim 1, wherein: the total weight ratio of the phenylalkyne to the epoxy compound is 1: 5 to 100.
4. The method for preparing alkynyl polyether according to claim 1, wherein: the copper catalyst is selected from copper salts, and the weight ratio of the copper catalyst to the phenylalkyne is 1: 10 to 100.
5. The method for preparing alkynyl polyether according to claim 4, wherein: the copper catalyst is selected from CuI, CuCl, CuBr and Cu2O、Cu(acac)2CuCl2、CuBr2、CuI2、Cu(OAc)2、Cu(OTf)2、Cu(ClO4)2Or CuSO4Any one of them.
6. The method for preparing alkynyl polyether according to claim 1, wherein: the base is selected from organic or inorganic base, the organic base is any one of triethylamine, 1, 8-diazabicycloundecen-7-ene and diisopropylethylamine, and the inorganic base is KOH and K2CO3、NaOH、Na2CO3、Cs2CO3、CsOH、K3PO4、K2HPO4、Na3PO4Or Na2HPO4In a weight ratio of base to phenylalkyne of 1: 10 to 100.
7. The method for preparing alkynyl polyether according to claim 1, wherein: weighing each reaction substance according to the weight fraction, adding phenyl alkyne, alkali and a copper catalyst into a reaction container at room temperature, introducing an epoxy compound, heating to 50-80 ℃ for polymerization, and reacting for 3-6 hours to obtain alkynyl polyether.
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