CN111440258B - Polyvinyl ether compound and preparation method thereof - Google Patents
Polyvinyl ether compound and preparation method thereof Download PDFInfo
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- CN111440258B CN111440258B CN202010359649.8A CN202010359649A CN111440258B CN 111440258 B CN111440258 B CN 111440258B CN 202010359649 A CN202010359649 A CN 202010359649A CN 111440258 B CN111440258 B CN 111440258B
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Abstract
The invention relates to a polyvinyl ether compound, wherein olefin polymers are covalently bonded in polyvinyl ether, and the structural formula is shown in the specificationThe following:
(ii) a Wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Both are aryl, alkyl with 1-13 carbon atoms or one of hydrogen atoms. The invention also discloses a preparation method of the compound. The invention has the advantages of no acetal structure, good chemical stability and low production cost.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a polyvinyl ether compound and a preparation method thereof.
Background
The polyvinyl ether lubricating oil has excellent lubricating property and good compatibility, and compared with lubricating oil such as poly-alpha olefin (PAO) lubricating oil and mineral oil, the polyvinyl ether lubricating oil has the advantages of large usable viscosity range, low pour point, high maximum non-seizure load and the like, thereby becoming an oil product with wide application background and being widely applied to lubricating oil viscosity index improvers, pour point depressants, refrigeration industry and other mechanical fields. However, the polyvinyl ether prepared at present has the defects of poor chemical stability, easy decomposition and discoloration when meeting acid and the like.
Polyvinyl ethers are generally obtained by cationic polymerization, and in order to control the molecular weight of the polyvinyl ether, compounds such as alcohol, water, acetal, etc. are generally added during the preparation process, so that the final product contains acetal structures, and the acetal and hemiacetal structures belong to unstable structures: under acidic conditions, the aldehyde is converted to the carboxylic acid. Therefore, in order to eliminate the acetal or hemiacetal structure in polyvinyl ether, it is common to obtain a stable compound by subjecting polyvinyl ether to a hydrogenation reaction at a high temperature (90 to 240 ℃) and a high pressure (5 to 15 MPa) under the catalysis of a catalyst such as a noble metal to eliminate the acetal or hemiacetal structure therein. The patent CN107216926A discloses a preparation method of polyvinyl ether lubricant base oil, which is to prepare polyvinyl ether by taking vinyl methyl ether and vinyl ethyl ether as raw materials under the conditions of 5-15 MPa of pressure and 100-200 ℃ of temperature and nickelThe hydrogenation reaction is completed under the catalysis of a catalyst of a series or noble metal, and finally, the product is obtained by distillation. Patent CN1182414A discloses a method for producing ether compounds, which adopts a catalyst containing nickel and inorganic oxides such as silicon oxide, magnesium oxide and the like at a temperature of 90-190 ℃ and a pressure of 3kg/cm2To 60kg/cm2Preparing the end ether polyvinyl ether by hydrogenolysis of the end acetal polyvinyl ether under the condition of (1), and finally obtaining the product by precipitation or filtration.
The method has the defects of expensive catalyst, harsh hydrogenation condition, high energy consumption, complex process and easy corrosion of equipment under high-temperature and high-pressure conditions.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyvinyl ether compound which does not contain an acetal structure and has good chemical stability and is terminated by an olefin polymer.
Another technical problem to be solved by the present invention is to provide a method for preparing the polyvinyl ether compound.
In order to solve the above problems, the present invention provides a polyvinyl ether compound, which is characterized in that: the olefin polymer in the compound is covalently bonded in polyvinyl ether, and the structural formula is as follows:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Both are aryl, alkyl with 1-13 carbon atoms or one of hydrogen atoms.
The process for producing a polyvinyl ether compound as described above is characterized in that: uniformly mixing an organic solvent, acetal-terminated polyvinyl ether and a cationic initiator, slowly adding olefin at the temperature of 0-25 ℃ under the condition of continuous stirring, reacting for 1-2 h, washing with water, and distilling to obtain an olefin polymer terminated polyvinyl ether compound; the adding amount of the organic solvent is 5-30% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the cationic initiator is 0.3-10% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the olefin is 0.8-27.8% of the mass of the polyvinyl ether containing acetal terminated end.
The acetal-terminated polyvinyl ether is one of polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl n-propyl ether, polyvinyl isopropyl ether, polyvinyl n-butyl ether, polyvinyl isobutyl ether, polyvinyl sec-butyl ether, polyvinyl tert-butyl ether, polyvinyl n-pentyl ether and polyvinyl n-hexyl ether, and the molecular weight of the acetal-terminated polyvinyl ether is 800-3000.
The cationic initiator is protonic acid or Lewis acid.
The protonic acid is concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid (HSO)3Cl), fluorosulfonic acid (HSO)3F) Trichloroacetic acid (CCl)3COOH), trifluoroacetic acid (CF)3COOH), trifluoromethanesulfonic acid (CF)3SO3H) One kind of (1).
The Lewis acid is boron trifluoride (BF)3) Aluminum trichloride (AlCl)3) Titanium tetrachloride (TiCl)4) Tin tetrachloride (SnCl)4) Zinc chloride (ZnCl)2) Antimony pentachloride (SbCl)5) One kind of (1).
The organic solvent is one of n-hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane and carbon tetrachloride.
The olefin is one of ethylene, propylene, 1-butene, 2-butene, isobutene, styrene, alpha-methyl styrene, butadiene, isoprene, hexene, 1-octene, 1-decene, dodecene and tetradecene.
Compared with the prior art, the invention has the following advantages:
1. the invention converts the polyvinyl ether terminated by acetal structure into olefin terminated polyvinyl ether, and improves the chemical stability of the polyvinyl ether.
2. The preparation method is simple and mild in condition, the synthesized polyvinyl ether does not need hydrogenation, the defects of expensive catalyst, harsh condition, high energy consumption, dangerous operation and the like in the traditional polyvinyl ether lubricating oil hydrogenation process are overcome, the production cost is effectively reduced, and the method can be widely applied to the field of refrigeration systems and other machinery.
Detailed Description
A polyvinyl ether compound in which an olefin polymer is covalently bonded to a polyvinyl ether, having the formula:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Both are aryl, alkyl with 1-13 carbon atoms or one of hydrogen atoms.
Example 1
Into a three-necked flask were charged 24g of n-hexane as a solvent, 80g (0.1 mol) of absolute ethanol-terminated polyvinyl methyl ether (M n= 800) and 8g of phosphoric acid, stirring and mixing uniformly, slowly introducing 1-butene, stirring at 0-25 ℃ for 1h, stopping, weighing to obtain 16g of introduced 1-butene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 2
A three-necked flask was charged with 20g of solvent n-hexane, 100g (0.1 mol) of methanol-terminated polyvinyl ethyl etherM n= 1000) and 1.5 g of boron trifluoride, stirring and mixing uniformly, slowly introducing isobutene, stirring for 1h at 0-25 ℃, stopping, weighing to obtain 27.8g of introduced isobutene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 3
In a three-neck flask were charged 20g of chloroform as a solvent, 120g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-propyl etherM n= 1200) and 0.9 g of aluminum trichloride, stirring and mixing uniformly, slowly introducing isoprene, stirring at 0-25 ℃ for 2h, stopping, and weighing to obtain introduced isopreneThe diene is 18.48g, and the product is obtained after water washing and rotary evaporation are carried out to remove impurities and unreacted substances.
Example 4
Into a three-necked flask were charged 27g of n-hexane as a solvent, 150g (0.1 mol) of anhydrous ethanol-terminated polyvinyl isopropyl etherM n= 1500) and 0.75 g sulfuric acid, stirring and mixing uniformly, slowly adding 1-octene, stirring at 0-25 ℃ for 2h, stopping, weighing to obtain 26.1g of added 1-octene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 5
Into a three-necked flask were charged 27g of chloroform as a solvent, 180g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-butyl etherM n= 1800) and 2.9 g of aluminum trichloride, stirring and mixing uniformly, slowly adding 1-decene, mechanically stirring at 0-25 ℃ for 1h, stopping, weighing to obtain 19.8g of added 1-decene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 6
Into a three-necked flask were charged 28g of n-hexane as a solvent, 200 g (0.1 mol) of anhydrous ethanol-terminated polyvinyl isobutyl etherM n= 2000) and 5.0 g of aluminum trichloride, stirring and mixing uniformly, slowly adding the dodecene, stirring for 2 hours at the temperature of 0-25 ℃, stopping, weighing to obtain 24.6g of added dodecene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 7
A three-necked flask was charged with 22g of n-hexane as a solvent, 220g (0.1 mol) of absolute ethanol-terminated polyvinyl sec-butyl ether (M n= 2200) and 0.66 g of boron trifluoride, stirring and mixing uniformly, slowly adding tetradecene, stirring for 2h at 0-25 ℃, stopping, weighing to obtain 28.38g of the added tetradecene, washing with water, and removing impurities and unreacted substances by rotary evaporation to obtain the product.
Example 8
Into a three-necked flask were charged 25g of n-hexane as a solvent, 250g (0.1 mol) of anhydrous ethanol-terminated poly (vinyl t-butyl ether) ((M n= 2500) and 5.25 g phosphoric acid, stirring and mixing evenlySlowly introducing 2-butene, stirring for 1.5h at 0-25 ℃, stopping, weighing to obtain 12.25g of introduced 2-butene, and washing with water and performing rotary evaporation to remove impurities and unreacted substances to obtain the product.
Example 9
Into a three-necked flask were charged 28g of chloroform as a solvent, 280g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-amyl etherM n= 2800) and 3.4 g of aluminum trichloride, stirring and mixing uniformly, slowly introducing ethylene, stirring at 0-25 ℃ for 2 hours, stopping, weighing to obtain 2.24g of introduced ethylene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 10
In a three-neck flask were charged 15g of solvent n-hexane, 300g (0.1 mol) of absolute ethanol-terminated polyvinyl n-hexyl ether (M n= 3000) and 5.5 g phosphoric acid, stirring and mixing uniformly, then slowly introducing propylene, stirring for 2h at 0-25 ℃, stopping, weighing to obtain 5.7g of introduced propylene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
In the above examples 1 to 10, the protonic acid may be concentrated sulfuric acid, perchloric acid, or chlorosulfonic acid (HSO)3Cl), fluorosulfonic acid (HSO)3F) Trichloroacetic acid (CCl)3COOH), trifluoroacetic acid (CF)3COOH), trifluoromethanesulfonic acid (CF)3SO3H) One kind of (1).
The Lewis acid may also be titanium tetrachloride (TiCl)4) Tin tetrachloride (SnCl)4) Zinc chloride (ZnCl)2) Antimony pentachloride (SbCl)5) One kind of (1).
The organic solvent can also adopt one of cyclohexane, dichloromethane, dichloroethane and carbon tetrachloride.
The olefin can also be one of styrene, alpha-methyl styrene, butadiene and hexene.
The product performances obtained in the above examples 1 to 10 are shown in table 1, and it can be seen that the examples 1 to 10 all have very low pour points and good compatibility.
Table 1 results of product performance tests obtained in examples 1 to 10
Although particular embodiments of the invention have been described and illustrated in detail, it should be understood that various equivalent changes and modifications could be made to the above-described embodiments in accordance with the present invention, and its functional effects could be achieved without departing from the spirit of the present invention.
Claims (7)
1. A polyvinyl ether compound characterized in that: the olefin polymer in the compound is covalently bonded in polyvinyl ether, and the structural formula is as follows:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Are one of aryl, alkyl with 1-13 carbon atoms or hydrogen atoms;
the preparation method comprises the following steps: uniformly mixing an organic solvent, acetal-terminated polyvinyl ether and a cationic initiator, slowly adding olefin at the temperature of 0-25 ℃ under the condition of continuous stirring, reacting for 1-2 h, washing with water, and distilling to obtain an olefin polymer terminated polyvinyl ether compound; the adding amount of the organic solvent is 5-30% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the cationic initiator is 0.3-10% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the olefin is 0.8-27.8% of the mass of the polyvinyl ether containing acetal terminated end.
2. The polyvinyl ether compound according to claim 1, wherein: the acetal-terminated polyvinyl ether is one of polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl n-propyl ether, polyvinyl isopropyl ether, polyvinyl n-butyl ether, polyvinyl isobutyl ether, polyvinyl sec-butyl ether, polyvinyl tert-butyl ether, polyvinyl n-pentyl ether and polyvinyl n-hexyl ether, and the molecular weight of the acetal-terminated polyvinyl ether is 800-3000.
3. The polyvinyl ether compound according to claim 1, wherein: the cationic initiator is protonic acid or Lewis acid.
4. The polyvinyl ether compound according to claim 3, wherein: the protonic acid is one of concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, trichloroacetic acid, trifluoroacetic acid and trifluoromethanesulfonic acid.
5. The polyvinyl ether compound according to claim 3, wherein: the Lewis acid is one of boron trifluoride, aluminum trichloride, titanium tetrachloride, stannic chloride, zinc chloride and antimony pentachloride.
6. The polyvinyl ether compound according to claim 1, wherein: the organic solvent is one of n-hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane and carbon tetrachloride.
7. The polyvinyl ether compound according to claim 1, wherein: the olefin is one of ethylene, propylene, 1-butene, 2-butene, isobutene, styrene, alpha-methyl styrene, butadiene, isoprene, hexene, 1-octene, 1-decene, dodecene and tetradecene.
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