CN110252411B - Complex platinum catalyst for producing epoxy-terminated silicone oil and preparation method and application thereof - Google Patents
Complex platinum catalyst for producing epoxy-terminated silicone oil and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
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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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Abstract
The invention discloses a complex type platinum catalyst for producing epoxy-terminated silicone oil, and a preparation method and application thereof, wherein the complex type platinum catalyst is an organic ligand-platinum complex obtained by a compound containing platinum (II), a first ligand and a second ligand through a complex reaction, the first ligand is at least one of tetramethyl divinyl disiloxane, acetylacetone or ethyl acetoacetate, and the second ligand is N, N '-bis (diphenylphosphino) piperazine or N, N' -bis (diphenylphosphinomethyl) piperazine. The complex platinum catalyst provided by the invention is used for producing epoxy-terminated silicone oil, can obtain high yield under extremely low consumption, has low product chromaticity, and can fully meet market requirements. The complex type platinum catalyst provided by the invention is simple to prepare, has cost similar to that of the traditional Karstedt catalyst, seems to greatly improve catalytic activity, can reduce the production cost of low-end epoxy silicone oil, and is a complex type platinum catalyst for producing the end epoxy silicone oil with great market competitiveness.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to a complex platinum catalyst for producing epoxy-terminated silicone oil, and a preparation method and application thereof.
Background
The epoxy modified silicone oil not only retains a plurality of excellent performances of the dimethyl silicone oil, but also has new functions of reactivity, adsorptivity, flexibility and the like. Therefore, the epoxy silicone oil has important application in the aspects of coating, fabric softening finishing, tackifying, resin modification and the like due to the characteristics. The traditional preparation method of the epoxy modified silicone oil comprises the following steps: (1) preparing an anionic or cationic emulsion by emulsion polymerization; (2) carrying out addition reaction on low-hydrogen silicone oil and a terminal alkenyl epoxy compound in the presence of a platinum catalyst to obtain a product; (3) the epoxy group coupling agent with bifunctional group and octamethylcyclotetrasilane or linear body are subjected to equilibrium condensation reaction to prepare the epoxy group coupling agentObtaining the product. The preparation of epoxy-modified silicone oils by addition is a common method, and in such methods, there are two types of catalysts used: the first generation catalyst is H2PtCl6·6H2O, Speier for the first time found that chloroplatinic acid was soluble in isopropanol, and this type of catalyst became a sebel catalyst. After this time, Willing reacted chloroplatinic acid with an unsaturated bond-containing siloxane compound based on the Speier method of use, and the catalyst formed after the reaction was more efficient. The second generation catalyst can be Karstedt (Karstedt) catalyst, Karstedt is based on the predecessor, and further improves the method of Willing, and the catalytic efficiency is further improved by using chloroplatinic acid or chloroplatinic acid salt to react with sodium bicarbonate and vinyl siloxane in ethanol under heating to form a platinum vinyl siloxane complex. Such catalysts are still used today in the organosilicon chemistry industry as the most commonly used catalyst in hydrosilylation reactions. However, the catalyst is unstable in storage, and is easy to react with heavy metal ions and other active compounds in a storage environment to form a new high-valence unstable platinum compound, and finally forms platinum black precipitate to lose catalytic activity. In addition, such catalysts are highly active and may react further with the epoxy groups in the product, producing undesirable isomerized by-products. Considering that chloroplatinic acid is very expensive, it is necessary to use as little catalyst as possible in industrial production. Therefore, a platinum catalyst with excellent activity is developed, the cost is reduced, and the industrial application value is very good.
Patent CN102516314A discloses a nitrogen heterocyclic carbene platinum complex catalyst, which is prepared by adding a nitrogen heterocyclic carbene ligand into a platinum catalyst, forming a platinum complex under certain reaction conditions, and utilizing steric hindrance effect and electronic effect formed by the nitrogen heterocyclic carbene to improve the activity of the catalyst. And in the synthesis of epoxy modified silicone oil, the epoxy group is easy to open the ring, so that the reaction process is severe and difficult to control, and further the product batches are different in quality and poor in consistency. If an inhibitor (1-ethynylcyclohexanol, etc.) is added, the color of the product is further darkened. In addition, the N-heterocyclic carbene platinum complex catalyst disclosed by the patent requires the premise of preparing N-heterocyclic carbene first, has a complex synthesis process, and is not suitable for large-scale industrial production. CN105854946B discloses a platinum-containing hydrosilylation catalyst, which comprises a platinum-containing compound and an organic ligand, wherein the organic ligand is a macrocyclic compound containing unsaturated bonds. Likewise, the synthesis process of such novel organic ligands is complex, expensive and not suitable for large-scale industrial production. Patent CN105797775B discloses a preparation method of vinyl platinum catalyst, which takes tetramethyl divinyl disiloxane or tetramethyl divinyl ring tetrasiloxane as ligand, alcohol solution of chloroplatinic acid reacts in the presence of sodium bicarbonate, and improves the conversion rate of chloroplatinic acid and the complexing yield of zero-valent platinum. Essentially Karstedt's catalyst is prepared in the patent, and the catalytic activity of the Karstedt's catalyst needs to be further improved.
In the case of heterogeneous catalysts, it is customary to immobilize the platinum on an inorganic support, as described, for example, in U.S. Pat. No. 3,2637738, DE2815316, CN 10597777B. However, such heterogeneous platinum catalysts still do not satisfy the industrial demands in terms of catalytic efficiency.
In view of the above deficiencies of the prior art, it is desirable to provide a catalyst with excellent comprehensive performance, which can improve the production efficiency of the epoxy silicone oil, and does not adversely affect the product, and at the same time, can reduce the production cost and simplify the production steps.
Disclosure of Invention
In order to solve the defects that the catalytic activity of the platinum catalyst for producing the epoxy-terminated silicone oil needs to be further improved and the product chromaticity is poor in the prior art, the invention aims to provide the complex type platinum catalyst for producing the epoxy-terminated silicone oil, which has high catalytic activity, can meet the production requirement of the epoxy-terminated silicone oil at an extremely low concentration of less than 2ppm, reduces the consumption of the catalyst, reduces the cost and further enables the chromaticity of the epoxy-terminated silicone oil to be lower.
The purpose of the invention is realized by the following technical scheme:
a complex type platinum catalyst for producing epoxy-terminated silicone oil is an organic ligand-platinum complex obtained by a complexation reaction of a compound containing platinum (II), a first ligand and a second ligand, wherein the first ligand is at least one of tetramethyldivinyldisiloxane, acetylacetone or ethyl acetoacetate, and the second ligand is N, N '-bis (diphenylphosphino) piperazine or N, N' -bis (diphenylphosphinomethyl) piperazine.
The platinum (II) -containing compound is not particularly limited as long as it can produce Pt (II) in the above system, and examples thereof include, but are not limited to, H2PtCl4、PtCl2、Na2PtCl4、K2PtCl4At least one of (1). The platinum (II) -containing compounds also include hydrates of the above compounds, such as Na2PtCl4·xH2O、K2PtCl4·xH2O and x are integers between 1 and 6.
Preferably, in the complex platinum catalyst, the mass ratio of the first ligand to the second ligand is 1:0.05 to 0.3, more preferably 1:0.1 to 0.2.
The invention also provides a preparation method of the complex type platinum catalyst for producing the epoxy-terminated silicone oil, which comprises the following steps: adding a certain amount of compound containing platinum (II), an acid-binding agent, a first ligand and a second ligand into an organic solvent, reacting for 3-6 hours at 40-60 ℃, filtering to remove the acid-binding agent after the reaction is finished, and then removing the solvent under the vacuum of-0.05 MPa to-0.10 MPa to prepare the complex platinum catalyst.
Preferably, the organic solvent is at least one of methanol, ethanol, N-propanol, isopropanol, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, acetone, ethyl acetate, dichloromethane, and chloroform.
The acid-binding agent is not particularly limited as long as it has a weakly basic substance and does not adversely affect the reaction system, and examples of the acid-binding agent include, but are not limited to, at least one of sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and pyridine.
Preferably, the mass ratio of the compound containing platinum (II), the acid-binding agent, the first ligand and the second ligand is 0.05-0.2: 0.1-0.5: 1-1.5: 0.05 to 0.3, more preferably 0.1 to 0.15: 0.15-0.3: 1: 0.1-0.2.
The invention also provides a method for producing the epoxy-terminated silicone oil, which comprises the following steps: under the action of the complex type platinum catalyst provided by the invention, the hydrogen-terminated silicone oil and the terminal alkenyl epoxide undergo Si-H addition reaction to obtain the terminal epoxy silicone oil.
The production steps of epoxy-terminated silicone oils are well known in the art and include the following specific steps: adding hydrogen-terminated silicone oil and a terminal alkenyl epoxy compound into a reaction vessel, adding the complex type platinum catalyst, stirring and reacting for 3-8 hours at 60-100 ℃, and keeping the temperature to remove low-boiling-point compounds to obtain the terminal epoxy silicone oil.
Preferably, the complex type platinum catalyst is used in an amount of 1.35 to 2.60ppm, more preferably 1.85 to 2.20ppm, in terms of platinum.
Preferably, the mass ratio of the hydrogen-terminated silicone oil to the alkenyl-terminated epoxy compound is 100:1-5, and preferably 100: 2-4.
Preferably, the terminal alkenyl epoxy compound is selected from Allyl Glycidyl Ether (AGE), cardanol glycidyl ether (NC-513), Glycidyl Methacrylate (GMA).
Compared with the prior art, the invention has the following beneficial effects:
the inventor unexpectedly finds that the catalytic efficiency is greatly improved by adding a small amount of second ligand, namely N, N '-bis (diphenylphosphino) piperazine or N, N' -bis (diphenylphosphinomethyl) piperazine, into a common complex platinum catalyst, namely a Speier type catalyst or a Karstedt type catalyst, the same catalytic efficiency can be achieved under the condition of less catalyst consumption, the cost is reduced, and the production efficiency is improved.
Secondly, the novel complex type platinum catalyst provided by the invention not only further improves the yield and the efficiency, but also obviously improves the chroma Hazen (Hazen) of the obtained epoxy-terminated silicone oil, and further widens the application range of the epoxy silicone oil product.
Detailed description of the preferred embodiments
The complex platinum catalyst of the present invention and the production of epoxy-terminated silicone oil using the catalyst are described below with reference to specific examples. In these examples, all fractions and percentages are by mass unless otherwise indicated.
The purity of the finished product is the mass percentage of the finished product.
The yield refers to the theoretical yield of the product obtained by conversion through chemical reaction and comparison, and is 100%. Wherein, the yield of the complex platinum catalyst preparation and the dosage of the catalyst in the system are calculated by taking platinum as a reference.
The raw material for producing the epoxy-terminated silicone oil of the invention contains 1.2 percent of active hydrogen by mass of hydrogen-containing silicone oil,
preparation example preparation of Complex type platinum Compound
Preparation example 1
2.00g PtCl2Adding the mixture into 10.13g of absolute ethyl alcohol, adding 2.56g of sodium bicarbonate, 18.73g of tetramethyldivinyldisiloxane and 2.32g N, N' -bis (diphenylphosphinomethyl) piperazine, reacting at 60 ℃ for 3-6 hours until the color of the sodium bicarbonate is changed into light yellow, filtering the sodium bicarbonate, and then removing the solvent at a vacuum degree of-0.08 MPa to prepare the complex platinum catalyst, wherein the yield is 95.3 percent based on platinum.
Preparation example 2
2.00g of PtCl2Adding 14.23g of tetrahydrofuran, adding 2.56g of sodium bicarbonate, 18.73g of acetylacetone and 2.32g of 2.32g N, N' -bis (diphenylphosphinomethyl) piperazine, reacting at 60 ℃ for 3-6 hours until the color of the sodium bicarbonate is changed into light yellow, filtering the sodium bicarbonate, and then removing the solvent at a vacuum degree of-0.06 MPa to prepare the complex type platinum catalyst, wherein the yield is 94.7 percent in terms of platinum.
Preparation example 3
2.00g of PtCl2Adding 14.23g of tetrahydrofuran, adding 2.56g of sodium bicarbonate, 18.73g of ethyl acetoacetate and 2.32. 2.32g N, N' -bis (diphenylphosphinomethyl) piperazine, reacting at 50 ℃ for 3-6 hours until the color of the sodium bicarbonate is changed into light yellow, filtering the sodium bicarbonate, and then removing the solvent under the vacuum degree of-0.07 MPa to prepare the complex type platinum catalyst, wherein the yield is 95.2 percent in terms of platinum.
Preparation examples 4 to 12
According to a similar method, complex platinum catalysts obtained by selecting different raw material ratios are shown in the following table 1:
TABLE 1
Preparation example of epoxy-terminated Silicone oil
Example 1
195g of hydrogen-terminated silicone oil and 5g of Allyl Glycidyl Ether (AGE) were added to a reaction vessel, the complex type platinum catalyst prepared in preparation example 1 was added, the amount of the platinum catalyst added was 1.85ppm (in terms of platinum) of the reaction system, and the reaction was stirred at 90 ℃ for 5 hours, followed by removal of low boiling point compounds while maintaining the temperature, to obtain epoxy-terminated silicone oil, the reaction conversion was 96%, and the product color was 14 Hazen.
Epoxy-terminated silicone oils were prepared in a similar manner using, as catalysts, complex-type platinum prepared in preparation examples 4 to 12 and comparative preparation examples 1 to 3, respectively, and the properties of the resulting products are shown in Table 2 below:
among them, the test method for the color blackness of the product-end epoxy silicone oil refers to GB3143, "method for measuring color of liquid chemical products (Hazen unit — platinum-cobalt color number)".
The test principle is as follows: in the chemical reagent base standard (1988), the color is expressed in terms of "Heizhong", and 1 Heizhong unit means a color containing 1mg of chloroplatinic acid (H) per liter2PtCl6) Platinum in the form and 2mg of cobalt chloride (CoCl)2·6H20) The color of the platinum-cobalt solution of (a). The potassium chloroplatinate, the platinum chloride and the hydrochloric acid are prepared into an aqueous solution (platinum-cobalt standard solution) according to a certain proportion, so that the color tone of the solution is similar to that of a sample to be detected under most conditions, and the chromaticity of the sample can be obtained by comparing the sample with the platinum-cobalt standard solution by a visual method.
The specific test method adopted in the embodiment of the invention is as follows:
1. 500 Hazen units of standard platinum-cobalt solutions were prepared.
Accurately weighing 2.000g of cobalt chloride and 2.491g of potassium chloroplatinate, dissolving in 200ml of hydrochloric acid and a proper amount of water, diluting to 2000ml, and shaking up to obtain the product.
2. Diluted platinum-cobalt standard solution (diluted platinum-cobalt standard solution should be prepared before use)
And (3) sucking platinum-cobalt standard solutions with different volumes of 500 Heiyang units, and diluting to 100ml to obtain diluted platinum-cobalt standard solutions with different Heiyang units.
3. The samples were visually compared to the platinum-cobalt standard solution to obtain the chromaticity of the samples.
TABLE 2
The data in table 2 show that when the complex platinum catalyst provided by the invention is used for producing hydrogen terminated silicone oil, the excellent catalytic efficiency can be achieved under the condition of very small addition amount, the yield reaches more than 94%, meanwhile, the product chromaticity is ensured to be low, and the chromaticity of the epoxy silicone oil at the end of the product is below 15-black. In the preferred embodiment of the invention, the yield can reach 99% under the condition that the dosage of the complex platinum catalyst is 1.85ppm of the system, and the chroma of the product is only 8 Hazen. In the comparative example, the catalytic activity was greatly reduced due to the use of the complex type platinum catalyst to which the second ligand was not added. If the similar production efficiency is to be achieved, a large amount of platinum catalyst is needed, on one hand, the cost of platinum is high, and on the other hand, the chroma is obviously improved due to the increase of the catalyst dosage, and the obtained product cannot meet the actual requirement.
The above embodiments are merely illustrative of the present disclosure and do not represent a limitation of the present disclosure. Other variations of the specific structure of the invention will occur to those skilled in the art.
Claims (11)
1. A complex platinum catalyst for producing epoxy-terminated silicone oil is an organic ligand-platinum complex obtained by a complexation reaction of a compound containing platinum (II), a first ligand and a second ligand, wherein the first ligand is at least one of tetramethyldivinyldisiloxane, acetylacetone or ethyl acetoacetate, and the second ligand is N, N '-bis (diphenylphosphino) piperazine or N, N' -bis (diphenylphosphinomethyl) piperazine;
the mass ratio of the first ligand to the second ligand is 1: 0.1-0.2.
2. The complex-type platinum catalyst according to claim 1, wherein the compound containing platinum (II) comprises H2PtCl4、PtCl2、Na2PtCl4、K2PtCl4At least one of (a); the platinum (II) -containing compounds also include hydrates of the above compounds, including Na2PtCl4·xH2O or K2PtCl4·xH2O and x are integers between 1 and 6.
3. The preparation method of the complex type platinum catalyst according to claim 1 or 2, comprising the steps of: adding a certain amount of compound containing platinum (II), an acid-binding agent, a first ligand and a second ligand into an organic solvent, reacting for 3-6 hours at 40-60 ℃, filtering to remove the acid-binding agent after the reaction is finished, and then removing the solvent under the vacuum of-0.05 MPa to-0.10 MPa to prepare the complex platinum catalyst.
4. The method according to claim 3, wherein the organic solvent is at least one of methanol, ethanol, N-propanol, isopropanol, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, acetone, ethyl acetate, dichloromethane, and chloroform; the acid-binding agent comprises at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and pyridine.
5. The method of claim 3, wherein the platinum (II) -containing compound, the acid-binding agent, the first ligand, and the second ligand are present in a mass ratio of 0.05 to 0.2: 0.1-0.5: 1-1.5: 0.05-0.3.
6. The method of claim 5, wherein the platinum (II) -containing compound, the acid-binding agent, the first ligand, and the second ligand are present in a mass ratio of 0.1 to 0.15: 0.15-0.3: 1: 0.1-0.2.
7. A method for producing epoxy-terminated silicone oil comprises the following steps: performing Si-H addition reaction on hydrogen-terminated silicone oil and terminal alkenyl epoxide under the action of a complex type platinum catalyst to obtain terminal epoxy silicone oil, wherein the complex type platinum catalyst is the complex type platinum catalyst in claim 1 or 2 or the complex type platinum catalyst prepared by the preparation method in any one of claims 3 to 6.
8. The method for producing epoxy-terminated silicone oil according to claim 7, comprising the steps of: adding hydrogen-terminated silicone oil and a terminal alkenyl epoxy compound into a reaction vessel, adding the complex type platinum catalyst, stirring and reacting for 3-8 hours at 60-100 ℃, and keeping the temperature to remove low-boiling-point compounds to obtain the terminal epoxy silicone oil.
9. The method for producing epoxy-terminated silicone oil according to claim 7 or 8, wherein the amount of the complex type platinum catalyst is 1.35 to 2.60ppm in terms of platinum; the mass ratio of the hydrogen-terminated silicone oil to the alkenyl-terminated epoxy compound is 100: 1-5.
10. The method for producing epoxy-terminated silicone oil according to claim 9, wherein the amount of the complex type platinum catalyst is 1.85 to 2.20ppm in terms of platinum, and the mass ratio of the hydrogen-terminated silicone oil to the alkenyl-terminated epoxy compound is 100:2 to 4.
11. The method for producing the epoxy-terminated silicone oil according to claim 7 or 8, wherein the terminal alkylene oxide compound is selected from allyl glycidyl ether, cardanol glycidyl ether, glycidyl methacrylate ether.
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| CN111072972A (en) * | 2019-12-14 | 2020-04-28 | 烟台开发区金宏化工有限公司 | Preparation method of epoxy-terminated silicone oil and application of epoxy-terminated silicone oil in amino silicone oil |
| CN114471726B (en) * | 2022-01-26 | 2023-12-29 | 淮安晨化新材料有限公司 | Preparation method and application of efficient catalyst for hydrosilylation reaction |
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