CN115109256A - Preparation method of block silicone oil with high flash point and low solvent content - Google Patents
Preparation method of block silicone oil with high flash point and low solvent content Download PDFInfo
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 115
- 239000002904 solvent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 45
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The invention belongs to the technical field of silicone oil synthesis, and particularly relates to a preparation method of block silicone oil with a high flash point and low solvent content. Epoxy ring-opening block polymerization is carried out on epoxy-terminated silicone oil and polyether amine in a high-flash-point organic solvent system such as diethylene glycol butyl ether and the like to prepare block silicone oil; compared with the traditional isopropanol solvent system, the method disclosed by the invention avoids using isopropanol with a low flash point, can complete the reaction only by using a small amount of organic solvent with a high flash point, can leave the solvent in the system as an auxiliary emulsifier, does not need post-treatment operations such as removal, replacement and the like, is simpler in synthesis process, low-carbon, energy-saving and safe, and avoids production operation and safety problems caused by using isopropanol in the production process.
Description
Technical Field
The invention belongs to the technical field of silicone oil synthesis, and particularly relates to a preparation method of block silicone oil with a high flash point and low solvent content.
Background
The block silicone oil is synthesized by the following method: epoxy silicone oil and amino polyether are used for reaction under the condition of isopropanol solvent. The synthetic methods disclosed in patents CN103214676A and CN111393654A are both prepared by using the method. The method has the characteristics of high reaction speed, low temperature and high conversion rate of raw materials, can be well suitable for the reaction of epoxy silicone oil with different molecular weights and amino polyether with different structures, and can synthesize block silicone oil with different application performances.
However, due to the physical characteristics of low flash point, flammability, explosiveness and volatility of isopropanol, great pressure is applied to production, storage and transportation of products, and in the face of ever-increasing environmental protection requirements, the dosage of isopropanol must be reduced or post-treatment procedures must be added to reduce the safety and environmental protection problems brought by isopropanol. At present, it is common to distill off the isopropanol or replace other solvents after the reaction is finished. The synthesis method disclosed in patent CN106319975A adds a post-treatment step, and adopts a method of distilling off isopropanol after the reaction is finished. But isopropanol residue is still inevitable, so that the flash point of a silicone oil product is lower, a post-treatment process for evaporating a solvent is added, the whole synthesis process is complicated and complicated, and the energy consumption is increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of block silicone oil with high flash point and low solvent content, which adopts a high flash point organic solvent to replace the traditional isopropanol solvent, synthesizes the block silicone oil by a one-step method, simplifies the synthesis process, improves the production efficiency, and solves the technical problems of potential safety hazard, complex and fussy operation process and the like caused by low flash point of the isopropanol solvent used for synthesizing the block silicone oil in the prior art.
In order to achieve the purpose, the invention provides a preparation method of block silicone oil with high flash point and low solvent content, which takes epoxy-terminated silicone oil and polyether amine as raw materials and takes a high flash point organic solvent as a reaction medium to carry out epoxy ring-opening block polymerization reaction to obtain the block silicone oil with high flash point and low solvent content.
Preferably, the high flash point organic solvent is one or more of dipropylene glycol butyl ether, ethylene glycol butyl ether and diethylene glycol butyl ether.
Further preferably, the high flash point organic solvent is diethylene glycol butyl ether.
Preferably, the epoxy-terminated silicone oil and polyetheramine are present in an epoxy: the molar ratio of amino groups is 1 (1.0-2.0) and the material is fed.
Preferably, the epoxy-terminated silicone oil is double-ended epoxy silicone oil with the average molecular weight of 1000-25000.
Preferably, the polyether amine is one or more of linear double-end amino polyether with the average molecular weight of 200-2003 and Y-type branched three-end amino polyether with the average molecular weight of 200-900.
Preferably, the epoxy-terminated silicone oil has an average molecular weight of less than 12000 and the polyetheramine has an average molecular weight of less than or equal to 900, and more preferably less than or equal to 600.
Preferably, the amount of the solvent is 5 to 25 percent of the total weight of the reaction system, and more preferably 10 to 15 percent.
Preferably, the reaction temperature of the epoxy ring-opening block polymerization reaction is 80-100 ℃, and the reaction time is 8-24 h.
Generally, compared with the prior art, the technical scheme conceived by the invention has the following beneficial effects:
(1) the invention adopts high flash point organic solvents such as diethylene glycol monobutyl ether and the like as reaction media to synthesize the block silicone oil by a one-step method, avoids using isopropanol and solvent post-treatment operation brought by the isopropanol, simplifies the synthesis process and improves the production efficiency.
(2) The block silicone oil synthesized by the invention has high flash point and low solvent content, and improves the safety of production, storage and transportation.
(3) In the preferred embodiment of the invention, diethylene glycol monobutyl ether is used as a reaction medium, epoxy-terminated silicone oil with proper molecular weight and polyether amine are used as raw materials, and a high-quality block silicone oil product with high epoxy conversion rate, no epoxy residue, high flash point and low solvent content is obtained through one-step reaction.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of block silicone oil according to the present invention;
FIG. 2 is a photograph of block silicone oil products prepared using different high flash point solvents according to examples 1 and 14 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of block silicone oil with high flash point and low solvent content, as shown in figure 1, epoxy-terminated silicone oil and polyether amine are used as raw materials, a high flash point organic solvent is used as a reaction medium, and epoxy ring-opening block polymerization reaction is carried out to obtain the block silicone oil with high flash point and low solvent content; wherein the high-flash-point organic solvent is one or more of dipropylene glycol butyl ether, ethylene glycol butyl ether and diethylene glycol butyl ether.
In some embodiments, the epoxy-terminated silicone oil and polyetheramine are present in an epoxy: the molar ratio of the amino groups is 1 (1.0-2.0) and the materials are fed. The epoxy-terminated silicone oil is double-ended epoxy silicone oil with the average molecular weight of 1000-25000.
In some embodiments, the polyether amine is one or more of a linear double-terminal amino polyether with an average molecular weight of 200-2003 or a Y-type branched three-terminal amino polyether with an average molecular weight of 200-900. Such as D230, D400, ED600, ED900, T403, etc.
In some embodiments, the solvent is used in an amount of 5% to 25%, preferably 10% to 15%, by weight of the total charge including solvent. The reaction temperature of the epoxy ring-opening reaction is 80-100 ℃, and the reaction time is 8-24 h.
The invention prepares the block silicone oil through the epoxy ring-opening reaction of the epoxy-terminated silicone oil and the polyether amine, and the function of the adopted high flash point organic solvent in the reaction not only plays the role of the solvent, but also plays the role of catalyzing the epoxy ring-opening. Experiments show that the reaction activity of the epoxy ring-opening reaction has certain difference when different high-flash-point organic solvents are adopted. The preferred solvent is diethylene glycol butyl ether. In the experimental process, the polyether amine with the average molecular weight of less than or equal to 900 (preferably less than or equal to 600) is found to have relatively highest epoxy ring-opening reaction activity with the epoxy-terminated silicone oil, so that the target product can be synthesized in a shorter time. Correspondingly, the high-flash-point organic solvent is more favorable for the ring-opening block reaction of the terminal epoxy silicone oil with the molecular weight of less than 12000, and experiments show that the epoxy conversion rate of the reaction is influenced by the poor solubility of the terminal epoxy silicone oil with the excessive molecular weight when the high-flash-point organic solvent is used for the reaction.
The epoxy-terminated silicone oil raw materials with different molecular weights adopted by the invention can be obtained according to a conventional synthesis method, and in some embodiments, the epoxy-terminated silicone oil raw materials are prepared by the following method: and (2) putting the hydrogen-terminated silicone oil and allyl glycidyl ether into a reaction bottle according to the molar ratio of 1: 1.0-1.2, carrying out hydrosilylation reaction under the catalysis of chloroplatinic acid, reacting for 4 hours at 80-100 ℃, and removing low-boiling-point substances to obtain the epoxy-terminated silicone oil.
The invention adopts epoxy-terminated silicone oil and polyether amine to carry out epoxy ring-opening block polymerization reaction in high flash point organic solvents such as diethylene glycol butyl ether and the like to obtain block silicone oil; compared with the traditional isopropanol solvent system, the method disclosed by the invention avoids the use of isopropanol with a low flash point, the reaction can be completed only by using a small amount of diethylene glycol butyl ether with a high flash point, the diethylene glycol butyl ether can be remained in the system as an auxiliary emulsifier, post-treatment operations such as solvent removal, solvent replacement and the like are not required, the synthetic process is simpler, low-carbon, energy-saving and safe, and a series of production operation and safety problems caused by the use of isopropanol in production are avoided.
The following are examples:
example 1
120g of epoxy-terminated silicone oil (average molecular weight 8000), 6.9g of polyetheramine D230 and 15g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 80 ℃ under stirring, and the reaction is performed under constant temperature reflux for 18h to obtain colorless, clear and transparent block silicone oil a 1.
Physical and chemical indexes of block silicone oil are as follows: epoxy content < 0.01mmol/g (indicating no detection); the epoxy conversion rate is 99.5%; a solids content of about 89%; the flash point is > 100 ℃.
Example 2
110g of epoxy-terminated silicone oil (average molecular weight 2000), 60g of polyetheramine ED900 and 40g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 100 ℃ under stirring, and the constant temperature reflux reaction is carried out for 24 hours, so that light yellow clear transparent block silicone oil a2 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 98.5%; a solids content of about 80%; the flash point is > 100 ℃.
Example 3
150g of epoxy-terminated silicone oil (average molecular weight: 15000), 3.5g of polyetheramine D230 and 17g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 80 ℃ under stirring, and the reaction is carried out under constant temperature and reflux for 20h, so that colorless, clear and transparent block silicone oil a3 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 98.2%; a solids content of about 90%; the flash point is > 100 ℃.
Example 4
100g of epoxy-terminated silicone oil (average molecular weight: 4000), 22.5g of polyetheramine ED600 and 30g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 90 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 24 hours to obtain light yellow clear transparent block silicone oil a 4.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 97.1%; a solids content of about 79%; the flash point is > 100 ℃.
Example 5
120g of epoxy-terminated silicone oil (average molecular weight 8000), 6g of polyetheramine T403 and 24g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 80 ℃ under stirring, and the reaction is carried out under constant temperature reflux for 8h, so that colorless, clear and transparent block silicone oil a5 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 95.3%; the solid content is about 83%; the flash point is > 100 ℃.
Example 6
100g of epoxy-terminated silicone oil (the average molecular weight is 5000), 4g of polyetheramine T403, 10g of polyetheramine ED900 and 25g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 90 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 20 hours, so as to obtain light yellow clear transparent block silicone oil a 6.
Physical and chemical indexes of block silicone oil: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 97.7%; a solids content of about 83%; the flash point is > 100 ℃.
Example 7
120g of epoxy-terminated silicone oil (average molecular weight is 6000), 24g of polyetheramine ED600 and 26g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 90 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 20 hours to obtain light yellow clear transparent block silicone oil a 7.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 96.0 percent; a solids content of about 85%; the flash point is > 100 ℃.
Example 8
120g of epoxy-terminated silicone oil (the average molecular weight is 10000), 5g of polyetheramine D230 and 15g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 90 ℃ under stirring, and the reflux reaction is carried out for 16h at constant temperature, so that colorless, clear and transparent block silicone oil a8 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 99.0%; a solids content of about 89%; the flash point is > 100 ℃.
Example 9
120g of epoxy-terminated silicone oil (average molecular weight: 5000), 5g of polyetheramine D230, 13g of polyetheramine ED900 and 25g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 100 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 24 hours, so as to obtain light yellow clear transparent block silicone oil a 9.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 97.3%; the solid content is about 83%; the flash point is > 100 ℃.
Example 10
20g of epoxy-terminated silicone oil (average molecular weight: 4000), 100g of epoxy-terminated silicone oil (average molecular weight: 12000), 5g of polyetheramine T403 and 20g of diethylene glycol butyl ether were put into a four-neck flask equipped with a reflux device and a thermometer, and heated to 80 ℃ with stirring, and subjected to constant-temperature reflux reaction for 15 hours to obtain colorless, clear and transparent block silicone oil a 10.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is 95.5%; a solids content of about 85%; the flash point is > 100 ℃.
Example 11
150g of epoxy-terminated silicone oil (average molecular weight 30000), 2g of polyetheramine D230 and 40g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 100 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 30 hours, so as to obtain yellow clear and transparent block silicone oil a 11.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is 0.025 mmol/g; the epoxy conversion rate is 62%; a solids content of about 78%; the flash point is > 100 ℃.
Example 12
150g of epoxy-terminated silicone oil (average molecular weight: 15000), 40g of polyetheramine ED2003 and 40g of diethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 100 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 24h to obtain yellow clear turbid block silicone oil a 12.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is 0.025 mmol/g; the epoxy conversion rate was 77%; a solids content of about 80%; the flash point is > 100 ℃.
Example 13
120g of terminal epoxy silicone oil (average molecular weight is 8000), 6.9g of polyetheramine D230 and 20g of dipropylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is increased to 80 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 20 hours to obtain faint yellow and turbid block silicone oil a 13.
Physical and chemical indexes of block silicone oil: the epoxy content is 0.025 mmol/g; the epoxy conversion rate is 90.2%; a solids content of about 85%; the flash point is > 100 ℃.
It is obvious from the above examples that diethylene glycol butyl ether is directly used as a solvent, and a block silicone oil product with epoxy conversion rate close to 100% and flash point higher than 100 ℃ can be synthesized; dipropylene glycol butyl ether may not exhibit as high a catalytic activity as diethylene glycol butyl ether due to differences in structure and solubility, resulting in a relatively low epoxy conversion and a hazy appearance. In addition, as can be seen from examples 9, 10, 11 and 12, the epoxy-terminated silicone oil and the polyetheramine have relatively high molecular weights, for example, when the molecular weight of the epoxy-terminated silicone oil is higher than or equal to 12000 and the molecular weight of the polyetheramine is higher than 900, the epoxy conversion rate of the reaction is reduced, corresponding to the epoxy residue in the obtained block silicone oil product.
Example 14
120g of epoxy-terminated silicone oil (average molecular weight 8000), 5g of polyetheramine D230 and 15g of ethylene glycol butyl ether are put into a four-neck flask provided with a reflux device and a thermometer, and heated to 80 ℃ under stirring to carry out constant-temperature reflux reaction for 18h, so that block silicone oil a14 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is 0.025 mmol/g; the epoxy conversion rate is 90.0%; a solids content of about 88%; the flash point is > 100 ℃.
Example 14 uses butyl cellosolve as a solvent and produces a block silicone oil that is slightly hazy in appearance (fig. 2, content (b)), with lower epoxy content and lower conversion than the block silicone oil of example 1, which was produced using butyl cellosolve (fig. 2, content (a)), probably due to the difference in polarity between butyl cellosolve and butyl cellosolve. When the block silicone oil product is applied, the detection is generally considered to be no detection if the concentration is less than 0.01mmol/g, and the detection of the epoxy content indicates that the epoxy and the polyether amine in the system do not completely react, so that the final polymer structure is changed, and the application performance of the product is directly influenced; meanwhile, the remaining unreacted epoxy groups in the system may also affect the stability of the product, such as the appearance of the product.
Comparative example 1
120g of epoxy-terminated silicone oil (average molecular weight 8000), 6.9g of polyetheramine D230 and 30g of isopropanol are put into a four-neck flask provided with a reflux device and a thermometer, the temperature is raised to 80 ℃ under stirring, and the constant-temperature reflux reaction is carried out for 12 hours, so that the non-clear and transparent block silicone oil b1 is obtained.
Physical and chemical indexes of block silicone oil are as follows: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is approximately equal to 100 percent; a solids content of about 80%; the flash point is less than 30 ℃.
Comparative example 2
110g of epoxy-terminated silicone oil (average molecular weight: 2000), 60g of polyetheramine ED900 and 50g of isopropanol are put into a four-neck flask provided with a reflux device and a thermometer, and heated to 80 ℃ with stirring, and subjected to constant-temperature reflux reaction for 20 hours to obtain colorless, clear and transparent block silicone oil b 2.
Physical and chemical indexes of block silicone oil: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is approximately equal to 100 percent; a solids content of about 75%; the flash point is less than 30 ℃.
It is readily apparent from comparative examples 1 and 2 that with the isopropanol reaction, the epoxy conversion is higher, but the flash point of the block silicone oil product is lower.
Comparative example 3
Putting 120g of epoxy silicone oil (average molecular weight is 8000), 6.9g of polyetheramine D230 and 30g of isopropanol into a four-neck flask provided with a reflux device and a thermometer, heating to 80 ℃ under stirring, and carrying out constant-temperature reflux reaction for 12 hours; then carrying out reduced pressure distillation to remove isopropanol, slightly cooling, and then adding 15g of diethylene glycol butyl ether into the distilled system to obtain colorless, clear and transparent block silicone oil b 3.
Physical and chemical indexes of block silicone oil: the epoxy content is less than 0.01 mmol/g; the epoxy conversion rate is approximately equal to 100 percent; a solids content of about 90%; the flash point is > 90 ℃.
Comparative example 3 although the solvent substitution was carried out with diethylene glycol butyl ether after the reaction, isopropanol remained inevitably in the product, which resulted in a silicone oil product having a flash point lower than that of the silicone oil products of examples, and the solvent substitution operation increased the production process.
Compared with the embodiment and the comparative example, the diethylene glycol butyl ether is used in the embodiment of the invention to complete the reaction in one step, post-treatment operations such as solvent removal, solvent replacement and the like are not needed, the synthesis process is simpler and safer, and the epoxy in the system is basically reacted completely.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A preparation method of block silicone oil with high flash point and low solvent content is characterized in that epoxy-terminated silicone oil and polyether amine are used as raw materials, a high flash point organic solvent is used as a reaction medium, and epoxy ring-opening block polymerization reaction is carried out to obtain the block silicone oil with high flash point and low solvent content.
2. The process of claim 1 wherein the high flash point organic solvent is one or more of dipropylene glycol butyl ether, ethylene glycol butyl ether, and diethylene glycol butyl ether.
3. The method of claim 1, wherein the epoxy-terminated silicone oil and polyetheramine are present in an epoxy: the molar ratio of amino groups is 1 (1.0-2.0) and the material is fed.
4. The method of claim 1, wherein the terminal epoxy silicone oil is a terminal epoxy silicone oil having an average molecular weight of 1000 to 25000.
5. The method of claim 1, wherein the polyetheramine is one or more of a linear, double-ended amino polyether having an average molecular weight of 200 to 2003 and a Y-branched, three-ended amino polyether having an average molecular weight of 200 to 900.
6. The method of claim 1, wherein the epoxy-terminated silicone oil has an average molecular weight of less than 12000 and the polyetheramine has an average molecular weight of less than or equal to 900.
7. The method according to claim 1, wherein the solvent is used in an amount of 5 to 25% by weight, preferably 10 to 15% by weight, based on the total weight of the reaction system.
8. The method of claim 1, wherein the epoxy ring-opening block polymerization reaction is carried out at a temperature of 80 to 100 ℃ for a time of 8 to 24 hours.
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|---|---|---|---|---|
| CN115612106A (en) * | 2022-11-07 | 2023-01-17 | 杭州传化精细化工有限公司 | Preparation method of efficient antibacterial finishing agent |
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| CN115895798A (en) * | 2022-11-11 | 2023-04-04 | 射阳天源化工有限公司 | Silicon-containing fabric cleaning agent and preparation method thereof |
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