CN112574428B - Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof - Google Patents
Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2229/04—Siloxanes with specific structure
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
- C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
Abstract
The invention discloses a fluorine-silicon-containing hyperbranched polymer which comprises the following components: mixing methyltriethoxysilane and diisopropanolamine, and adding p-toluenesulfonic acid to perform catalytic reaction to obtain a hydroxyl-terminated hyperbranched polymer containing a siloxane structure; dissolving hexafluoropropylene tripolymer and p-hydroxybenzoic acid in N, N-dimethylformamide, dropwise adding triethylamine to obtain p-hydroxybenzoic acid hexafluoropropylene tripolymer, and reacting with hydroxyl-terminated hyperbranched polymer containing siloxane structure to obtain the fluorine-containing silicon hyperbranched polymer. The invention also discloses a mold release agent containing the fluorine-containing silicon hyperbranched polymer, which comprises the following raw materials in parts by weight: 6-10 parts of fluorine-containing silicon hyperbranched polymer, 30-40 parts of emulsifier, 1-3 parts of ethyl acetate, 8-10 parts of silicone oil and 60-80 parts of deionized water. The product of the invention can improve the demoulding effect and heat resistance of the demoulding agent, prevent the demoulding agent from deteriorating at high temperature, ensure the product quality and clean moulds and improve the production efficiency.
Description
Technical Field
The invention relates to the technical field of release agents, and particularly relates to a hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof.
Background
The rubber release agent is one of various categories of release agents, acts between a mold and rubber, completely separates a cured and molded product from the mold, prevents the phenomena of tearing, adhesion and the like, ensures the product quality, enables the mold to be used for multiple times, and avoids frequent cleaning. As an important functional auxiliary agent in rubber production, the rubber release agent must have high temperature resistance, and because the vulcanization process of rubber often needs to be carried out at high temperature, for example, the vulcanization temperature of the hot vulcanized silicone rubber is 200 ℃ to 230 ℃, the release agent needs to have high temperature resistance so as to ensure that the rubber can be smoothly released after being vulcanized. The traditional release agent comprises powder release agent, wax oil, soap and the like, but the high-temperature resistance of the traditional release agent is poor, the release agent can be changed in quality when the vulcanization temperature is high, the release effect is greatly weakened or even completely lost, and the release agent and a product are adhered and adsorbed, so that the mold and the product are polluted, the product can be torn even possibly, and the product quality and the production efficiency are seriously influenced.
Currently, the release agents on the market mainly include wax-based release agents, silicone-based release agents, and fluorine-based release agents. In view of the role of fluorine and silicon in mold release agents, fluorine-containing silicon mold release agents are now emerging, and patent 201610040811.3 discloses a fluorosilicone mold release agent composition using a fluorosilicone compound as a main raw material. The compound has a small number of branches, limits the number of fluorine and silicon atoms, and also limits the mold release effect when used as a mold release agent. The hyperbranched polymer is a macromolecular polymer, has a simple preparation method, and also has the advantages of high branching degree, less intermolecular chain entanglement, rich active sites, good solubility, high thermal stability and the like. Therefore, a hyperbranched polymer is needed, fluorine and silicon are introduced into the hyperbranched polymer, so that the tail end of the hyperbranched polymer contains a large amount of fluorine and silicon, and the fluorine-containing silicon hyperbranched polymer is used for preparing the release agent so as to improve the release effect and the heat resistance of the release agent.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a hyperbranched fluorine-containing silicon high-temperature resistant release agent. The product of the invention can well improve the demoulding effect and heat resistance of the demoulding agent and prevent the demoulding agent from quality change at high temperature, thereby ensuring the product quality and the mould cleanness and improving the production efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a fluorine-containing silicon hyperbranched polymer prepared by the steps of:
(1) mixing methyltriethoxysilane and diisopropanolamine, and adding p-toluenesulfonic acid to perform catalytic reaction to obtain a hydroxyl-terminated hyperbranched polymer containing a siloxane structure;
(2) and (2) dissolving hexafluoropropylene trimer and p-hydroxybenzoic acid in N, N-dimethylformamide, dropwise adding triethylamine to obtain p-hydroxybenzoic acid hexafluoropropylene trimer, and reacting the p-hydroxybenzoic acid hexafluoropropylene trimer with the siloxane structure-containing hydroxyl-terminated hyperbranched polymer obtained in the step (1) to obtain the fluorine-containing silicon hyperbranched polymer.
Preferably, in the step (1), the molar ratio of the methyltriethoxysilane to the diisopropanolamine is (4-94): (9-189); the total addition amount of the p-toluenesulfonic acid is 0.5 percent of the total mass of the methyltriethoxysilane and the diisopropanolamine.
More preferably, the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 4:9 to obtain a second-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 10:21 to obtain a third-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 22:45 to obtain a fourth-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 46:93 to obtain a fifth-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 94:189 to obtain the sixth generation hydroxyl-terminated hyperbranched polymer.
Preferably, in the step (1), the conditions of the catalytic reaction are as follows: heating for 2h at 100 ℃ under the protection of nitrogen; then, the nitrogen introduction was stopped, and the mixture was distilled under reduced pressure at 110 ℃ for 2 hours.
Preferably, in the step (2), the molar ratio of the hexafluoropropylene trimer, the p-hydroxybenzoic acid and the triethylamine is 1:1: 1.
Preferably, in the step (2), the triethylamine is stirred and reacted for 6 hours at room temperature after the triethylamine is added dropwise.
Preferably, in the step (2), the molar ratio of the hydroxyl-terminated hyperbranched polymer containing siloxane structures to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1: (6-96).
More preferably, the molar ratio of the second-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:6 to obtain a second-generation fluorine-containing silicon hyperbranched polymer; the molar ratio of the third-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:12 to obtain a third-generation fluorine-containing silicon hyperbranched polymer; the molar ratio of the fourth-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:24, so that a fourth-generation fluorine-containing silicon hyperbranched polymer is obtained; the molar ratio of the fifth-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene tripolymer is 1:48, so that a fifth-generation fluorine-containing silicon hyperbranched polymer is obtained; the molar ratio of the sixth generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene tripolymer is 1:96, so that the sixth generation fluorine-containing silicon hyperbranched polymer is obtained.
Preferably, in the step (2), the reaction conditions of the p-hydroxybenzoic acid hexafluoropropylene trimer and the hydroxyl-terminated hyperbranched polymer containing siloxane structure are as follows: heating for 2h at 140 ℃ under the protection of nitrogen; then, the nitrogen introduction was stopped, and distillation was carried out at 140 ℃ under reduced pressure for 2 hours.
The invention also provides an application of the fluorine-containing silicon hyperbranched polymer in preparation of a high-temperature-resistant release agent, wherein the high-temperature-resistant release agent is a hyperbranched fluorine-containing silicon high-temperature-resistant release agent.
The third aspect of the invention provides a hyperbranched fluorine-containing silicon high-temperature resistant release agent, which is characterized by comprising the following raw materials in parts by weight:
6-10 parts of fluorine-containing silicon hyperbranched polymer, 30-40 parts of emulsifier, 1-3 parts of ethyl acetate, 8-10 parts of silicone oil and 60-80 parts of deionized water.
Preferably, the feed comprises the following raw materials in parts by weight:
8 parts of fluorinated silicone hyperbranched polymer, 45 parts of emulsifier, 2 parts of ethyl acetate, 9 parts of silicone oil and 70 parts of deionized water.
Preferably, the feed comprises the following raw materials in parts by weight:
8 parts of fourth-generation fluorine-containing silicon hyperbranched polymer, 45 parts of emulsifier, 2 parts of ethyl acetate, 9 parts of silicone oil and 70 parts of deionized water.
Preferably, the emulsifier is at least one selected from OP-10, sodium dodecyl sulfate, OP-7 and Tween 80.
Preferably, the emulsifier is obtained by mixing OP-10 and sodium dodecyl sulfate according to the mass ratio of 23: 12.
The fourth aspect of the invention provides an application of the hyperbranched fluorine-containing silicon high-temperature resistant release agent in rubber demolding.
The invention has the beneficial effects that:
1. the hyperbranched polymer prepared by the invention is of a three-dimensional network structure, has a stable structure and a plurality of active sites, a small amount of hyperbranched polymer contains a large amount of fluorine elements and silicon elements, the rubber release agent prepared by the hyperbranched polymer also contains a large amount of fluorine elements and silicon elements, the fluorine elements can effectively reduce the surface tension of a coating film and can also improve the stability of the coating film, the silicon elements can improve the high temperature resistance of the release agent, the release effect is obviously improved, and the hyperbranched polymer has no corrosion to a mold, is not easy to pollute the mold and prolongs the cleaning period of the mold, thereby improving the production efficiency.
2. The preparation method is simple and has good demolding effect, and the product is suitable for being widely applied to the demolding field such as rubber demolding and the like as the demolding agent.
Drawings
FIG. 1 is a second generation of fluorinated silicone-containing hyperbranched polymers;
FIG. 2 is a third generation of a hyperbranched polymer containing fluorine and silicon;
FIG. 3 is a fourth generation fluorosilicone hyperbranched polymer:
FIG. 4 is a fifth generation fluorosilicone hyperbranched polymer;
FIG. 5 is a sixth generation fluorosilicone hyperbranched polymer;
wherein:
represents Si;
represents an F-containing group.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As introduced in the background art, the fluorosilicone mold release agent appears in view of the effects of fluorine and silicon in the mold release agent, but the compound has few branched chains and contains fewer fluorine atoms and silicon atoms, so that the fluorosilicone compound cannot have a good mold release effect and has poor temperature resistance.
Based on the above, the invention aims to provide the fluorine-silicon-containing hyperbranched polymer, which is compounded with the emulsifier, ethyl acetate, silicone oil and deionized water to obtain the release agent with high temperature resistance and good release effect. The specific synthetic method of the fluorine-silicon-containing hyperbranched polymer comprises the following steps:
(1) synthesis of hydroxyl-terminated hyperbranched polymer
(2) Synthesis of p-hydroxybenzoic acid hexafluoropropylene trimer
(3) Synthesis of fluorine-silicon-containing hyperbranched polymer
And (3) obtaining a second-generation hydroxyl-terminated hyperbranched polymer, a third-generation hydroxyl-terminated hyperbranched polymer, a fourth-generation hydroxyl-terminated hyperbranched polymer, a fifth-generation hydroxyl-terminated hyperbranched polymer and a sixth-generation hydroxyl-terminated hyperbranched polymer by adjusting the molar ratio of the methyltriethoxysilane to the diisopropanol. And then, respectively adjusting the molar ratios of the second-generation, third-generation, fourth-generation, fifth-generation and sixth-generation hydroxyl-terminated hyperbranched polymers to p-hydroxybenzoic acid hexafluoropropylene tripolymers to obtain products, namely a second-generation fluorinated silicone hyperbranched polymer, a third-generation fluorinated silicone hyperbranched polymer, a fourth-generation fluorinated silicone hyperbranched polymer, a fifth-generation fluorinated silicone hyperbranched polymer and a sixth-generation fluorinated silicone hyperbranched polymer, wherein the structural schematic diagrams are shown in fig. 1-5.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Example 1
13.813g of p-hydroxybenzoic acid and 45.007g of hexafluoropropylene trimer were weighed into a three-necked flask, 200ml of N, N-dimethylformamide was added, a mechanical stirrer was mounted on the three-necked flask, and stirred at room temperature to dissolve all the reactants, 10.119g of triethylamine was slowly added dropwise, and after the addition was completed, the reaction was stirred at room temperature for 6 hours. And after the reaction is finished, pouring the reaction liquid into excessive dilute hydrochloric acid for precipitation, filtering, washing the filtered precipitate with water, and finally drying the precipitate in a vacuum drying oven at 100 ℃ until the weight of the precipitate is constant to obtain the p-hydroxybenzoic acid hexafluoropropylene trimer.
Example 2
(1) Weighing 1.783g of methyltriethoxysilane, 3.996g of diisopropanolamine and 0.0289g of p-toluenesulfonic acid, adding the methyl triethoxysilane, 3.996g of diisopropanolamine and 0.0289g of p-toluenesulfonic acid into a three-neck flask, respectively installing a mechanical stirrer, a reflux condenser tube and a nitrogen gas inlet tube on the three-neck flask, placing the three-neck flask into an oil bath pot, opening condensed water, reacting for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 100 ℃, then closing the reflux condenser tube, vacuumizing under reduced pressure, keeping stirring, continuing to react for 2 hours at 110 ℃, closing a vacuum pump, adding 5.349g of methyltriethoxysilane, 7.991g of diisopropanolamine and 0.0667g of p-toluenesulfonic acid into the flask, opening the condensed water, reacting for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 100 ℃, then closing the nitrogen gas, taking off the reflux condenser tube, vacuumizing under reduced pressure, keeping stirring, continuing to react for 2 hours at 110 ℃, closing the vacuum pump, transferring the substances in the flask to an evaporation dish, and (3) placing the evaporating dish in a vacuum drying oven at 60 ℃ for vacuum drying for 5h to obtain the second-generation hydroxyl-terminated hyperbranched polymer.
(2) 10.567g of second-generation hydroxyl-terminated hyperbranched polymer and 27.004g of p-hydroxybenzoic acid hexafluoropropylene trimer prepared by the method in example 1 are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the mixture reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring and 140 ℃ continue to react for 2 hours, a vacuum pump is closed, and the reaction liquid is cooled to room temperature to obtain the second-generation fluorine-containing hyperbranched polymer.
(3) Fully stirring and mixing 8Kg of second-generation fluorinated silicon-containing hyperbranched polymer, 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water to prepare the second-generation hyperbranched fluorine-containing silicon high-temperature resistant release agent.
Example 3
(1) On the basis of synthesizing a second-generation hydroxyl-terminated hyperbranched polymer, 10.698g of methyltriethoxysilane, 15.983g of diisopropanolamine and 0.0.133g of p-toluenesulfonic acid are weighed and added into a three-neck flask, a mechanical stirrer, a reflux condenser tube and a nitrogen introduction tube are respectively installed on the three-neck flask, the three-neck flask is placed into an oil bath pot, condensed water is opened, the three-neck flask is mechanically stirred, reacts for 2 hours under the dry nitrogen atmosphere and 100 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, the stirring and 110 ℃ are kept for continuous reaction for 2 hours, a vacuum pump is closed, substances in the flask are transferred into an evaporation dish, and the evaporation dish is placed in a vacuum drying box at 60 ℃ for vacuum drying for 5 hours to obtain a third-generation hydroxyl-terminated hyperbranched polymer.
(2) 21.134g of third-generation hydroxyl-terminated hyperbranched polymer and 54.008g of p-hydroxybenzoic acid hexafluoropropylene trimer prepared by the method of example 1 are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the reaction is carried out for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, the vacuum pumping is carried out under reduced pressure, the stirring and the continuous reaction is carried out for 2 hours at 140 ℃, a vacuum pump is closed, and the reaction liquid is cooled to room temperature, so that the third-generation fluorine-containing hyperbranched polymer is obtained.
(3) Fully stirring and mixing 8Kg of third-generation fluorinated silicon-containing hyperbranched polymer, 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water to prepare the third-generation hyperbranched fluorine-containing silicon high-temperature resistant release agent.
Example 4
(1) On the basis of synthesizing the third-generation hydroxyl-terminated hyperbranched polymer, 21.396g of methyltriethoxysilane, 31.966g of diisopropanolamine and 0.267g of p-toluenesulfonic acid are weighed and added into a three-neck flask, a mechanical stirrer, a reflux condenser tube and a nitrogen introduction tube are respectively installed on the three-neck flask, the three-neck flask is placed into an oil bath pot, condensed water is opened, the three-neck flask is mechanically stirred, reacts for 2 hours under the dry nitrogen atmosphere and 100 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring and 110 ℃ are kept for continuous reaction for 2 hours, a vacuum pump is closed, substances in the flask are transferred into an evaporation dish, and the evaporation dish is placed in a vacuum drying box at 60 ℃ for vacuum drying for 5 hours to obtain the fourth-generation hydroxyl-terminated hyperbranched polymer.
(2) 21.135g of fourth-generation hydroxyl-terminated hyperbranched polymer and 54.008g of p-hydroxybenzoic acid hexafluoropropylene trimer prepared by the method of example 1 are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the mixture reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring is kept, the mixture continues to react for 2 hours at 140 ℃, a vacuum pump is closed, and the reaction liquid is cooled to room temperature to obtain the fourth-generation fluorine-containing silicon hyperbranched polymer.
(3) Fully stirring and mixing 8Kg of fourth generation fluorinated silicone hyperbranched polymer, 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water to prepare the fourth generation hyperbranched fluorinated silicone high-temperature resistant release agent.
Example 5
(1) On the basis of synthesizing a hydroxyl-terminated hyperbranched polymer of the fourth generation, 42.792g of methyltriethoxysilane, 63.931g of diisopropanolamine and 0.534g of p-toluenesulfonic acid are weighed and added into a three-neck flask, a mechanical stirrer, a reflux condenser tube and a nitrogen inlet tube are respectively installed on the three-neck flask, the three-neck flask is placed into an oil bath pot, condensed water is opened, the three-neck flask reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 100 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring and 110 ℃ are kept for continuous reaction for 2 hours, a vacuum pump is closed, substances in the flask are transferred into an evaporating dish, and the evaporating dish is placed in a vacuum drying box at 60 ℃ for vacuum drying for 5 hours to obtain the hydroxyl-terminated hyperbranched polymer of the fifth generation.
(2) 42.269g of fifth-generation hydroxyl-terminated hyperbranched polymer and 108.017g of p-hydroxybenzoic acid hexafluoropropylene trimer prepared by the method of example 1 are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the mixture reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring is kept, the mixture continues to react for 2 hours at 140 ℃, a vacuum pump is closed, and the reaction liquid is cooled to room temperature to obtain the fifth-generation fluorine-containing silicon hyperbranched polymer.
(3) Fully stirring and mixing 8Kg of fifth generation fluorinated silicon hyperbranched polymer with 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water to prepare the fifth generation hyperbranched fluorinated silicon high-temperature resistant release agent.
Example 6
(1) On the basis of synthesizing a hydroxyl-terminated hyperbranched polymer of the fifth generation, 85.584g of methyltriethoxysilane, 127.862g of diisopropanolamine and 1.068g of p-toluenesulfonic acid are weighed and added into a three-neck flask, a mechanical stirrer, a reflux condenser tube and a nitrogen inlet tube are respectively installed on the three-neck flask, the three-neck flask is placed into an oil bath pot, condensed water is opened, the three-neck flask reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 100 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring is kept, the temperature of 110 ℃ is kept, the reaction continues for 2 hours, a vacuum pump is closed, substances in the flask are transferred into an evaporation dish, and the evaporation dish is placed in a vacuum drying box at 60 ℃ to be dried for 5 hours under vacuum to obtain the hydroxyl-terminated hyperbranched polymer of the sixth generation.
(2) 28.179g of sixth-generation hydroxyl-terminated hyperbranched polymer and 72.011g of p-hydroxybenzoic acid hexafluoropropylene trimer prepared by the method of example 1 are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the mixture reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, vacuum pumping is carried out under reduced pressure, stirring is kept, the mixture continues to react for 2 hours at 140 ℃, a vacuum pump is closed, and the reaction liquid is cooled to room temperature to obtain the sixth-generation fluorine-containing silicon hyperbranched polymer.
(3) 8Kg of sixth generation fluorinated silicon hyperbranched polymer, 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water are fully stirred and mixed to prepare the sixth generation hyperbranched fluorinated silicon high-temperature resistant release agent.
Comparative example 1
(1) Weighing 14.82g of triethoxymethane, 39.957g of diisopropanolamine and 0.274g of p-toluenesulfonic acid, adding into a three-neck flask, respectively installing a mechanical stirrer, a reflux condenser tube and a nitrogen inlet tube on the three-neck flask, then placing the three-neck flask into an oil bath pot, opening condensed water, reacting for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 100 ℃, then closing nitrogen, taking off the reflux condenser tube, vacuumizing under reduced pressure, keeping stirring, continuing to react for 2 hours at 110 ℃, turning off a vacuum pump, transferring substances in the flask into an evaporating dish, placing the evaporating dish in a vacuum drying oven at 60 ℃ for vacuum drying for 5 hours to obtain the hydroxyl-terminated hyperbranched polymer.
(2) Weighing 40.956g of hydroxyl-terminated hyperbranched polymer and 174.667g of p-hydroxybenzoic acid hexafluoropropylene trimer, putting the hydroxyl-terminated hyperbranched polymer and the p-hydroxybenzoic acid hexafluoropropylene trimer into a three-neck flask provided with a stirrer, a reflux condenser pipe and a nitrogen inlet pipe, putting the three-neck flask into an oil bath pot, opening condensed water, reacting for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then closing the nitrogen, taking the reflux condenser pipe down, reducing pressure and vacuumizing, keeping stirring, continuing to react for 2 hours at 140 ℃, closing a vacuum pump, and cooling the reaction liquid to room temperature to obtain the fluorine-containing hyperbranched polymer.
(3) 8Kg of fluorine-containing hyperbranched polymer, 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water are fully stirred and mixed to prepare the hyperbranched fluorine-containing release agent.
Comparative example 2
(1) 13.319g of diisopropanolamine and 116.444g of p-hydroxybenzoic acid hexafluoropropylene trimer are weighed and put into a three-neck flask provided with a stirrer, a reflux condenser tube and a nitrogen inlet tube, then the three-neck flask is put into an oil bath pot, condensed water is opened, the three-neck flask reacts for 2 hours under the conditions of mechanical stirring, dry nitrogen atmosphere and 140 ℃, then the nitrogen is closed, the reflux condenser tube is taken down, the pressure is reduced, the vacuum pumping is carried out, the stirring is kept, the 140 ℃ continues to react for 2 hours, a vacuum pump is closed, and the reaction liquid is cooled to the room temperature, so that the fluorine-containing silicon polymer is obtained.
(2) 8Kg of fluorine-containing silicon polymer is fully stirred and mixed with 23Kg of OP-10, 12Kg of sodium dodecyl sulfate, 2Kg of ethyl acetate, 9Kg of silicone oil and 70Kg of deionized water to prepare the fluorine-containing silicon release agent.
Comparative example 3
The release agent was formulated according to the method of example 1 in patent application No. 201610040811.3:
95 parts by mass of a fluorosilicone compound 1 and 5 parts by mass of dodecyltrimethoxysilane were dissolved in 900 parts by mass of a solvent to prepare a mold release composition 1. Wherein the solvent adopts hexane: petroleum ether (boiling point 30-60 ℃): isopropanol is 2:2:1 (mass ratio).
The fluorosilicone compound was prepared according to the method of synthesis example 1:
25g of octafluoropentyl allyl ether (CH2 ═ CHCH2OCH2CF2CF2CF2CF2H), 1.6g of vinyltrimethoxysilane (CH2 ═ CHSi (OCH3)3) and 40g of toluene were added to a 250ml four-neck flask equipped with a mechanical stirring device, a thermometer, a condenser and a dropping funnel, 15mg of Pt (added in the form of a complex of Pt and 1, 2-divinyltetramethyldisiloxane) was added, the temperature was raised to 90 ℃, 19g of 0.5% trimethylsilyl-terminated hydrogen-containing silicone oil was slowly added dropwise, the dropping was completed in one hour, after the completion of the addition, the reaction was carried out at 90 ℃ for 7 hours, and then the solvent and unreacted monomers were removed by vacuum suction to obtain a fluorosilicone compound.
Comparative example 4
Commercially available fluorosilicone mold release agents: release agent GW-8000, available from tauao plastic materials ltd, of dongguan, au, by au industries co.
Comparative example 5
Commercial silicone release agents:
TNE50, available from Foshan Sheng Chuangda chemical Co.
Test examples
The release agents of examples 2 to 6 and the release agents of comparative examples 1 to 4 were subjected to a release test, and in the case of a rubber pipe made of styrene-butadiene rubber, styrene-butadiene rubber was fed into a carbon steel mold and vulcanized and molded at a certain temperature, pressure and time. Completely stripping rubber from a carbon steel mold after vulcanization molding is recorded as one-time complete demolding, if the rubber product is adhered to the mold or the rubber product is damaged, the rubber product cannot be regarded as complete demolding, and the times of complete demolding after one-time spraying of the demolding agent are recorded (the dosage of each group of the demolding agent is the same); after the first spraying, no release agent is sprayed, a rubber demolding test is continued, and after the last complete demolding, whether the surface of the mold is smooth or not is observed, namely whether the mold is polluted or corroded or not; the mold release agent is sprayed on the surface of the mold, the mold is heated after film formation, and when the film is deteriorated (appearance is changed, for example, smoke is generated), the heating is stopped, and the temperature at this time is referred to as the deterioration temperature of the mold release agent. Recording the times of complete demoulding of the demoulding agent after one-time spraying, observing the surface condition of the mould after demoulding, spraying the demoulding agent on the surface of the mould, heating, and recording the temperature of the demoulding agent when the demoulding agent is changed in quality (the appearance of a coating is changed). The results are shown in Table 1.
TABLE 1 Release agent Performance test
As can be seen from Table 1: (1) the high-temperature resistant rubber release agent produced in the embodiment of the invention has the advantages that the quality change temperature exceeds 250 ℃ because the hyperbranched polymer added into the release agent contains a polysiloxane structure, the Si-O bond in the polysiloxane has higher energy and is not easy to break at high temperature, so that the high-temperature resistant performance of the polysiloxane is excellent, the hyperbranched polymer has high branching degree and contains a large amount of siloxane structures, and the release agent produced by the invention has high quality change temperature and obvious high-temperature resistant effect, and the performance test results of a comparative example 1 (with hyperbranched but without silicon) and a comparative example 2 (with silicon but without hyperbranched) also show the point. (2) The number of times of complete demoulding of the rubber mould release agent produced by the invention in one-time spraying is more than that of the rubber mould release agent in comparative examples 1-5, because the hyperbranched polymer added into the mould release agent contains a large amount of fluorine elements, the surface tension of a coating can be effectively reduced, and the stability of the coating is improved. (3) The demolding effect and the high-temperature resistance of the embodiment of the invention are better than those of comparative examples 1-5, and the demolding agent containing the fourth-generation fluorine-containing silicon hyperbranched polymer (embodiment 4) is the best, because the fourth-generation fluorine-containing silicon hyperbranched polymer has more fluorine elements and silicon elements compared with the second-generation fluorine-containing silicon hyperbranched polymer and the third-generation fluorine-containing silicon hyperbranched polymer; although the fifth-generation and sixth-generation fluorine-silicon-containing hyperbranched polymers have more fluorine elements and silicon elements, because the branching degree is too high, part of the structures are wrapped by molecular chains, and the number of actually exerted functions is not much different from that of the fourth-generation fluorine-silicon-containing hyperbranched polymers. (4) The surface of the mold after the high-temperature resistant rubber mold release agent produced by the invention is demolded for many times is still smooth.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (11)
1. A fluorine-silicon-containing hyperbranched polymer is characterized by being prepared by the following steps:
(1) mixing methyltriethoxysilane and diisopropanolamine, and adding p-toluenesulfonic acid to perform catalytic reaction to obtain a hydroxyl-terminated hyperbranched polymer containing a siloxane structure;
(2) and (2) dissolving hexafluoropropylene trimer and p-hydroxybenzoic acid in N, N-dimethylformamide, dropwise adding triethylamine to obtain p-hydroxybenzoic acid hexafluoropropylene trimer, and reacting the p-hydroxybenzoic acid hexafluoropropylene trimer with the siloxane structure-containing hydroxyl-terminated hyperbranched polymer obtained in the step (1) to obtain the fluorine-containing silicon hyperbranched polymer.
2. The fluorine-silicon containing hyperbranched polymer according to claim 1, wherein in the step (1), the molar ratio of the methyltriethoxysilane to the diisopropanolamine is (4-94): (9-189); the total addition amount of the p-toluenesulfonic acid is 0.5 percent of the total mass of the methyltriethoxysilane and the diisopropanolamine.
3. The fluorinated silicon hyperbranched polymer according to claim 1, wherein in step (1), the conditions of the catalytic reaction are as follows: heating for 2h at 100 ℃ under the protection of nitrogen; then, the nitrogen introduction was stopped, and the mixture was distilled under reduced pressure at 110 ℃ for 2 hours.
4. The fluorinated silicon hyperbranched polymer according to claim 1, wherein in step (2), the molar ratio of hexafluoropropylene trimer, p-hydroxybenzoic acid and triethylamine is 1:1: 1.
5. The fluorinated silicon hyperbranched polymer according to claim 1, wherein in step (2), the molar ratio of the hydroxyl-terminated hyperbranched polymer containing siloxane structures to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1: (6-96).
6. The fluorinated silicon hyperbranched polymer according to claim 2 or 5, wherein the molar ratio of methyltriethoxysilane to diisopropanolamine is 4:9 to obtain a second generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 10:21 to obtain a third-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 22:45 to obtain a fourth-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 46:93 to obtain a fifth-generation hydroxyl-terminated hyperbranched polymer; the molar ratio of the methyltriethoxysilane to the diisopropanolamine is 94:189 to obtain the sixth generation hydroxyl-terminated hyperbranched polymer.
7. The fluorinated silicon hyperbranched polymer according to claim 6, wherein the molar ratio of the second generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:6 to obtain a second generation fluorinated silicon hyperbranched polymer; the molar ratio of the third-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:12 to obtain a third-generation fluorine-containing silicon hyperbranched polymer; the molar ratio of the fourth-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene trimer is 1:24, so that a fourth-generation fluorine-containing silicon hyperbranched polymer is obtained; the molar ratio of the fifth-generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene tripolymer is 1:48, so that a fifth-generation fluorine-containing silicon hyperbranched polymer is obtained; the molar ratio of the sixth generation hydroxyl-terminated hyperbranched polymer to the p-hydroxybenzoic acid hexafluoropropylene tripolymer is 1:96, so that the sixth generation fluorine-containing silicon hyperbranched polymer is obtained.
8. The application of the fluorine-containing silicon hyperbranched polymer as claimed in any one of claims 1 to 7 in preparing a high-temperature-resistant mold release agent, wherein the high-temperature-resistant mold release agent is a hyperbranched fluorine-containing silicon high-temperature-resistant mold release agent.
9. The hyperbranched fluorine-containing silicon high-temperature-resistant release agent is characterized by comprising the following raw materials in parts by weight:
6-10 parts of the fluorine-containing silicon hyperbranched polymer as defined in any one of claims 1-7, 30-40 parts of an emulsifier, 1-3 parts of ethyl acetate, 8-10 parts of silicone oil and 60-80 parts of deionized water;
the emulsifier is at least one selected from OP-10, sodium dodecyl sulfate, OP-7 and Tween 80.
10. The hyperbranched fluorine-containing silicon high-temperature resistant mold release agent as claimed in claim 9, which is characterized by comprising the following raw materials in parts by weight:
8 parts of the fourth-generation fluorine-containing silicon hyperbranched polymer, 45 parts of an emulsifier, 2 parts of ethyl acetate, 9 parts of silicone oil and 70 parts of deionized water;
the emulsifier is obtained by mixing OP-10 and sodium dodecyl sulfate according to the mass ratio of 23: 12.
11. Use of the hyperbranched fluorine-containing silicon high-temperature resistant mold release agent as claimed in claim 9 or 10 in rubber mold release.
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