CN111848956A - Polysiloxane with end group of phenolic group and preparation method thereof - Google Patents
Polysiloxane with end group of phenolic group and preparation method thereof Download PDFInfo
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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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The invention provides polysiloxane with a phenolic end group and a preparation method thereof, wherein the content of free allyl-containing phenol is less than 100ppm, the capping rate of the phenolic end group is more than 98 percent, and metal platinum does not exist. The preparation method comprises the following steps: a) catalyzing tetramethyldisiloxane and a phenolic compound containing allyl by using a transition metal catalyst to react to prepare an end-capping agent with a phenolic group as an end group; b) separating by reduced pressure distillation to obtain pure end capping agent with end group of phenolic group; c) under the condition of an acid catalyst, the pure end capping agent with the end group of the phenol group and silane ring bodies are subjected to ring-opening polymerization to obtain the polysiloxane with the end group of the phenol group. The polysiloxane with the phenolic group at the tail end has the advantages of high end capping rate, low free phenol content, low platinum content and the like.
Description
Technical Field
The invention relates to a preparation method of a polycarbonate modifier, in particular to polysiloxane with a phenolic group as an end group and a preparation method thereof.
Background
Polycarbonates have excellent mechanical properties such as transparency and impact resistance, and are widely used in the fields of automobiles, electronics, electric appliances, and the like. In order to improve the properties of polycarbonate such as flame retardancy and impact resistance, it has been reported in the literature that a polysiloxane-polycarbonate copolymer is prepared using a polysiloxane as a comonomer.
The method for modifying polycarbonate by polysiloxane reported in the literature at present comprises three steps: 1. synthesizing polysiloxane with silicon-hydrogen bond as the end group; 2. adopting platinum catalyst to catalyze hydrosilylation to synthesize polysiloxane with end group being phenolic group; 3. the polysiloxane with the end group of phenolic group is used as a comonomer to participate in the synthesis of the modified polycarbonate. The current synthesis method has the problem that the content of platinum and free phenol in the polysiloxane with the end group of phenol group is too high, and the problem can cause the polysiloxane-polycarbonate copolymer to be easy to yellow.
Patent CN104837896 reports a method for preparing a terminal phenol polysiloxane, which uses an activated carbon filter to adsorb platinum in the terminal phenol polysiloxane, and can obtain the terminal phenol polysiloxane with platinum content less than 0.9 ppm. However, the free phenol content of the polysiloxane with the end group of phenol prepared by the synthesis process in the patent can not be effectively reduced.
Patent CN105121515 reports a method for preparing a polysiloxane with terminal phenolic groups, which uses an adsorbent with an average pore diameter of less than 100 nm to adsorb platinum in the polysiloxane with terminal phenolic groups, and the result shows that 95% of the platinum in the product can be removed. However, the content of free phenol in the polysiloxane with the terminal group of phenol prepared by the method cannot be effectively reduced.
Patent CN102652149 reports a method for reducing free phenol in end group phenolic polysiloxane products, which can obtain products with free phenol content less than 100ppm after three times of washing with 0.3mol/L NaOH solution. However, this patent does not mention how to reduce the platinum content in the terminal phenol-based polysiloxane, resulting in a product that is susceptible to yellowing.
Therefore, there is a need to propose a new preparation process to reduce the platinum and free phenol content in the product.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel method for preparing polysiloxane with a terminal group of phenolic group. The polysiloxane with the end group of phenol prepared by the method has the characteristics of zero platinum content, low free phenol content and high end-capping rate.
The invention is realized by the following technical scheme:
a novel process for preparing a polysiloxane having terminal phenolic groups, comprising the steps of:
a) catalyzing tetramethyldisiloxane and a phenolic compound containing allyl by using a transition metal catalyst to react to prepare an end-capping agent with a phenolic group as an end group;
b) separating by reduced pressure distillation to obtain pure end capping agent with end group of phenolic group;
c) under the condition of an acid catalyst, the pure end capping agent with the end group of the phenol group and silane ring bodies are subjected to ring-opening polymerization to obtain the polysiloxane with the end group of the phenol group.
The invention discloses polysiloxane with a phenolic terminal group, which has a chemical structural formula shown as a formula (I) or a formula (II):
in the formula (I), the substitution positions of OH groups on phenyl groups at two ends of the molecule are respectively and independently ortho-position or para-position;
wherein R is1、R2Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a trifluoropropyl group, an aryl group having 6 to 12 carbon atoms, n is an integer > 0, preferably 5 or more, more preferably n is an integer between 10 and 500;
wherein R is1、R2And n is as defined for formula (I);
in the polysiloxane with the terminal group of phenolic group, the content of free phenol containing allyl is less than 100ppm, the capping rate of the phenolic group is more than 98 percent, and no metal platinum exists.
In the method, the end group in the step a) is an end-capping agent of a phenol group, and the structure of the end-capping agent is shown as a formula (III) or a formula (IV).
In the step a), the molar ratio of the tetramethyldisiloxane to the allyl-containing phenolic compound is 1:2-2.5, when the tetramethyldisiloxane is too much, the end-capping cannot be effectively carried out, and when the tetramethyldisiloxane is too little, the waste of raw materials is caused.
The reaction temperature of the step a) is 30-100 ℃, preferably 60-90 ℃, the catalyst can be deactivated when the reaction temperature is too high, and the reaction speed is too slow when the reaction temperature is too low; the reaction time is 2-10h, preferably 4-9h, and the blocking rate is too low due to too short reaction time.
Preferably, the transition metal catalyst in step a) is selected from one or more platinum-containing catalysts selected from chloroplatinic acid, vinylsiloxane-platinum complexes (e.g. tetramethyldivinyldisiloxane-platinum complex, tetramethyltetravinylcyclotetrasiloxane-platinum complex). The transition metal catalyst is used in an amount of 1 to 20ppm, preferably 2 to 15ppm, based on the sum of the masses of tetramethyldisiloxane and the allyl group-containing phenolic compound, based on the platinum in the catalyst.
Preferably, the allyl-containing phenolic compound in step a) is selected from one or more of 2-allylphenol, 4-allylphenol, eugenol, and the like.
The reduced pressure distillation in the step b) aims at obtaining pure end-capping agent with the end group of phenolic group by reduced pressure distillation, and preferably short path distillation is adopted to realize the separation process, and the reduced pressure distillation condition is 190 ℃ and 210 ℃ (20-50 Pa).
In said step c), the molar ratio of the silane ring body to the terminal phenol group-containing blocking agent is not particularly limited, and the specific molar ratio can be determined by the designed molecular weight of the polysiloxane, such as a molar ratio of 1 to 1000: 1, preferably the molar ratio is chosen to be 2-100: 1.
In the step c), the reaction temperature is 30-100 ℃, preferably 50-80 ℃, the reaction temperature is too low, the reaction is slow, and the catalyst is easy to yellow when the reaction temperature is too high; the reaction time is 4-48h, preferably 6-24h, and the silane ring conversion rate is too low when the reaction time is too short.
Preferably, the acidic catalyst in step c) is selected from one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, acidic cationic resins (e.g., polystyrenesulfonic acid resins, polyacrylic acid sulfonic acid resins), and the like, and more preferably, the acidic catalyst is selected from one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, acidic cationic resins, and the like. The amount of the acidic catalyst used is from 0.01 to 0.5% by weight, based on the sum of the mass of the end-capping agent having a phenolic group as the end group and the silane ring body in step c.
Preferably, the silane ring body of step c) is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, 1,3, 5-trimethylcyclotrisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltris (trifluoropropyl) cyclotrisiloxane, tetramethyltetrakis (trifluoropropyl) cyclotetrasiloxane, siloxane mixed ring body (DMC), etc.; more preferably, the silane ring body is selected from octamethylcyclotetrasiloxane, and siloxane mixed ring bodies.
After the reaction in step c) is completed, the acidic catalyst can be neutralized, then the low boiling point compound (such as unreacted siloxane ring body and micromolecular siloxane) can be separated by purification modes such as reduced pressure distillation and the like to obtain the pure polysiloxane with the end group of phenol group, and the conditions of the reduced pressure distillation can be-0.09 to-0.1 MPa, and the low boiling point compound can be removed by distillation at the temperature of 150 ℃ and 180 ℃ for 2 to 6 hours. The neutralizing agent used for neutralization can be calcium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate.
In the method, the end capping agent with the end group of phenolic group is prepared firstly, and then the end capping agent is purified and then is subjected to ring-opening polymerization with the silane ring body to obtain the silicone oil with the end group of phenolic group. The process can effectively separate the end capping agent with the end group of phenolic group from the platinum catalyst and the free phenol in the stage of reduced pressure distillation and purification to obtain the pure end capping agent, thereby avoiding the problem that the platinum catalyst and the free phenol are difficult to remove after the macromolecular polysiloxane is prepared by the traditional process, greatly reducing the content of the platinum catalyst and the content of the free phenol in the product, reducing the content of the free phenol to be less than 100ppm, and reducing the content of the platinum catalyst to be 0.
The polysiloxane with the terminal phenolic group prepared by the invention can be used as a comonomer for preparing the polysiloxane-polycarbonate copolymer.
The invention has the beneficial effects that:
1. the process of the invention fundamentally removes the platinum catalyst and reduces the content of free phenol, and the blocking agent can be purified in the separation stage, thereby avoiding the problem of blocking rate reduction caused by incomplete blocking.
2. The polysiloxane with the end group of the phenol group prepared by the process has the characteristics of zero platinum content, low free phenol content and high end-capping rate.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the examples, the test methods for free phenol: performing High Performance Liquid Chromatography (HPLC) with toluene as mobile phase; test method of platinum metal: using inductively coupled plasma mass spectrometry(ICP-MS) for measurement; end capping rate test method: using nuclear magnetic resonance (29Si-NMR).
Sources of raw materials in examples: (in the examples, the raw materials were purchased from Sigma-Aldrich)
Example 1
400 parts of eugenol (mass parts, the same below) and a Kanst catalyst (5 ppm of the total amount of the eugenol and the tetramethyldisiloxane in terms of platinum) are added into a 1L three-neck flask, the temperature is raised to 70 ℃, 150 parts of tetramethyldisiloxane is slowly dripped, and the reaction is continued for 4 hours after the dripping is finished. After the reaction is finished, reduced pressure distillation is carried out by using short-path evaporation equipment, and the fraction with the pressure of 192 ℃ and 195 ℃ is extracted to obtain the end-capping reagent (I).
40 parts of end-capping agent (I) is taken as a raw material, 500 parts of octamethylcyclotetrasiloxane and 0.5 part of trifluoromethanesulfonic acid are added, and equilibrium reaction is carried out at 60 ℃ for 8 hours. After the reaction is finished, 1 part of calcium carbonate is added to neutralize trifluoromethanesulfonic acid in the system, then clear transparent oily liquid is obtained by filtration, the obtained product is subjected to reduced pressure distillation to remove unreacted siloxane ring bodies and micromolecular siloxane under the condition of 160 ℃/-0.096MPa/3h, and the temperature is reduced to obtain oily polysiloxane (I). The resulting product polysiloxane (I) was determined to have a free phenol content of <100ppm, no platinum metal was detected, and a phenol-based capping rate of 98.1%.
Example 2
400 parts of o-allylphenol and a Kanst catalyst (10 ppm equivalent of the sum of the weights of the o-allylphenol and the tetramethyldisiloxane in terms of platinum) are added into a 1L three-neck flask, the temperature is raised to 50 ℃, 190 parts of tetramethyldisiloxane is slowly dripped, and the reaction is continued for 4 hours after the dripping is finished. After the reaction is finished, reduced pressure distillation is carried out by using short-path evaporation equipment, and the fraction with the pressure of 190-192 ℃ under 30Pa is extracted to obtain the end-capping reagent (II).
Taking 36 parts of end capping agent (II) as a raw material, adding 500 parts of siloxane mixed ring body (DMC) and 0.5 part of trifluoromethanesulfonic acid, and carrying out equilibrium reaction at 80 ℃ for 4 h. After the reaction is finished, 1 part of calcium carbonate is added to neutralize trifluoromethanesulfonic acid in the system, then clear transparent oily liquid is obtained by filtration, the obtained product is subjected to reduced pressure distillation to remove unreacted siloxane ring bodies and micromolecular siloxane under the condition of 160 ℃/-0.095MPa/4h, and the temperature is reduced to obtain oily polysiloxane (II). The resulting product polysiloxane (II) was determined to have a free phenol content of <100ppm, no platinum metal was detected, and a phenol-based capping rate of 98.7%.
Example 3
400 parts of p-allylphenol and a Kanst catalyst (10 ppm of the total amount of the p-allylphenol and the tetramethyldisiloxane in terms of platinum) are added into a 1L three-neck flask, the temperature is raised to 80 ℃, 150 parts of tetramethyldisiloxane is slowly dripped, and the reaction is continued for 6 hours after the dripping is finished. After the reaction is finished, reduced pressure distillation is carried out by using a short-path evaporation device, and the fraction with the pressure of 195-197 ℃ at 40Pa is extracted to obtain the end-capping reagent (III).
Taking 20 parts of end-capping agent (III) as a raw material, adding 500 parts of octamethylcyclotetrasiloxane and 1 part of trifluoromethanesulfonic acid, and carrying out equilibrium reaction at 80 ℃ for 6 h. After the reaction is finished, 2 parts of calcium carbonate is added to neutralize trifluoromethanesulfonic acid in the system, then clear transparent oily liquid is obtained by filtration, the obtained product is subjected to reduced pressure distillation to remove unreacted siloxane ring bodies and micromolecular siloxane under the condition of 170 ℃ and/or 0.09MPa/6h, and the temperature is reduced to obtain oily polysiloxane (III). The resulting product polysiloxane (III) was determined to have a free phenol content of <100ppm, no platinum metal was detected, and a phenol-based capping rate of 98.3%.
Comparative example 1
Taking 20 parts of tetramethyl disiloxane as a raw material, adding 500 parts of octamethylcyclotetrasiloxane and 0.5 part of trifluoromethanesulfonic acid, and carrying out equilibrium reaction at 60 ℃ for 8 hours. After the reaction is finished, 1 part of calcium carbonate is added to neutralize trifluoromethanesulfonic acid in the system, then clear transparent oily liquid is obtained by filtration, the obtained product is subjected to reduced pressure distillation to remove unreacted siloxane ring bodies and micromolecular siloxane under the condition of 160 ℃/-0.095MPa/2h, and the temperature is reduced to obtain oily polysiloxane (IV).
500 parts of polysiloxane (IV), 50 parts of eugenol and 5ppm of Karster catalyst (calculated as platinum) are added into a reactor and reacted for 4 hours at 50 ℃. After the reaction is completed, the free phenol is distilled off under reduced pressure to obtain polysiloxane (V) with the end group of phenol group. The resulting product polysiloxane (V) was determined to have a free phenol content of 1000ppm, a metal platinum content of 5ppm, and a phenol-based capping rate of 96.2%.
Claims (10)
1. A polysiloxane with a phenolic end group is characterized in that the chemical structural formula is shown as a formula (I) or a formula (II),
wherein R is1、R2Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a trifluoropropyl group, or an aryl group having 6 to 12 carbon atoms, and n is an integer > 0, preferably 5 or more, more preferably 10 to 500;
in the formula (I), the substitution positions of OH groups on phenyl groups at two ends of the molecule are respectively and independently ortho-position or para-position;
in the polysiloxane with the terminal group of phenolic group, the content of free phenol containing allyl is less than 100ppm, the capping rate of the phenolic group is more than 98 percent, and no metal platinum exists.
2. A method for producing the polysiloxane having a terminal phenolic group of claim 1, comprising the steps of:
a) in the presence of a catalyst A, reacting tetramethyldisiloxane with a phenolic compound containing allyl to prepare an end-capping agent with a phenolic group as an end group;
b) separating to obtain a pure end capping agent with a phenolic group as an end group;
c) in the presence of the catalyst B, the pure end capping agent with the end group of phenolic group and silane ring body are subjected to ring-opening polymerization to obtain the polysiloxane with the end group of phenolic group.
3. The method of claim 2, wherein the catalyst A of step a) is a transition metal catalyst comprising one or more platinum-containing catalysts selected from the group consisting of chloroplatinic acid, vinylsiloxane-platinum complex,
The transition metal catalyst is used in an amount of 1 to 20ppm, preferably 2 to 15ppm, based on the sum of the masses of tetramethyldisiloxane and the allyl-containing phenolic compound, based on the platinum in the catalyst.
4. The method of any one of claims 2-3, wherein the allyl-containing phenolic compound of step a) comprises 2-allylphenol, 4-allylphenol, eugenol.
5. The process according to any one of claims 2 to 4, wherein the molar ratio of tetramethyldisiloxane to the allyl-containing phenolic compound in step a) is from 1:2 to 2.5.
6. The process according to any one of claims 2 to 5, wherein the reaction temperature in step a) is from 30 to 100 ℃, preferably from 60 to 90 ℃, and the reaction time is from 2 to 10 hours, preferably from 4 to 9 hours.
7. The process of claim 2, wherein the separation in step b) is distillation under reduced pressure.
8. The process according to claim 2, wherein the catalyst B in step c) is an acidic catalyst comprising concentrated sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, an acidic cationic resin, preferably concentrated sulfuric acid, trifluoromethanesulfonic acid, an acidic cationic resin.
9. The method of claim 2 or 8, wherein the silane ring body of step c) comprises one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, 1,3, 5-trimethylcyclotrisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltris (trifluoropropyl) cyclotrisiloxane, tetramethyltetrakis (trifluoropropyl) cyclotetrasiloxane, a mixed ring body of siloxanes, preferably octamethylcyclotetrasiloxane, a mixed ring body of siloxanes.
10. The process according to any one of claims 2 to 9, wherein the reaction temperature in step c) is between 30 and 100 ℃, preferably between 50 and 80 ℃, and the reaction time is between 4 and 48h, preferably between 6 and 24 h.
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| CN115011118A (en) * | 2022-06-01 | 2022-09-06 | 江南大学 | Maleimide resin-based composition for packaging third-generation semiconductor device |
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