CN108059722A - A kind of polyarylether-polysiloxane copolymer and preparation method thereof - Google Patents
A kind of polyarylether-polysiloxane copolymer and preparation method thereof Download PDFInfo
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- CN108059722A CN108059722A CN201711415555.2A CN201711415555A CN108059722A CN 108059722 A CN108059722 A CN 108059722A CN 201711415555 A CN201711415555 A CN 201711415555A CN 108059722 A CN108059722 A CN 108059722A
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- GWTZJNMIPVEAFS-ZJDJEFGOSA-N CC[C@](C)(C(C)(C)C(C=C(C1OC(C)(C)C)c2ccccc2)=CC1c1ccccc1)Oc1c(C)cc(C(C)(C)O)cc1C Chemical compound CC[C@](C)(C(C)(C)C(C=C(C1OC(C)(C)C)c2ccccc2)=CC1c1ccccc1)Oc1c(C)cc(C(C)(C)O)cc1C GWTZJNMIPVEAFS-ZJDJEFGOSA-N 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N Cc1cccc(C)c1C Chemical compound Cc1cccc(C)c1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to silicone industry technical fields, to solve the deficiencies in the prior art, the present invention provides a kind of polyarylether polysiloxane copolymer and preparation method thereof, be using phenolic hydroxyl group sealing end polyarylether and hydrogen terminated polysiloxane as raw material, utilize catalytic dehydrogenation condensation methods, the Si H keys for making polysiloxane molecule chain end by catalyst activate, so that dehydrogenation coupling reaction occurs for two kinds of raw materials, polycondensation forms (AB) of compound with regular structurenType segmented copolymer, soft/hard section be by Si O Ph key connections together, obtained (AB)nType polyarylether polysiloxanes segmented copolymer has good mechanical property, heat resistance and oil resistant, solvent resistance.
Description
Technical field
The present invention relates to silicone industry technical fields, are specifically a kind of polyarylether-polysiloxane copolymer and its preparation
Method.
Background technology
Polysiloxane-based material has many unique and excellent performances, thus is obtained in the numerous areas of national economy
Extensive use, it has also become the indispensable important high molecular material of one kind of modern society.But since polysiloxane molecule chain is flexible
Higher (especially polydimethylsiloxane), needs in practical application to add in vulcanizing agent and is vulcanized, so that poly- silica
Reaction, the rubber for forming tridimensional network are crosslinked between alkane strand, also needs to add in filler (such as gas phase SiO in addition2
Deng) reinforcement is carried out, to improve its mechanical strength, expand application range.
Before and after the 1970s, with the further investigation to polysiloxane copolymer synthetic method and physical property, open
It has issued a kind of new organosilicon macromolecule material --- " thermoplastic silicone elastomers ".It need not add reinforcement and fill out
Material, it is not required that be chemically crosslinked using vulcanizing agent, need to be only molded by hot pressing, extrusion, injection or solution-cast, you can system
The product of different shapes such as sheet, membranaceous is obtained, product also recoverable, this is opened for the development of organosilicon macromolecule material
One brand-new road.
Thermoplastic silicone elastomers can be divided into two kinds of polyaddition type and condensation polymer type, on molecular structure according to synthetic method
Mostly based on block copolymer, particularly (AB)nType block copolymer, it is alternately common by rigid chain segment A and soft segment B
It is poly- to form.Its flexible portion is rubber constituent, the property for the body that demonstrates flexibility；Rigid element is plastic components, is dispersed in
In continuous polysiloxane molecule chain, play the role of reinforced filling.This structure also determines that the analog copolymer has two
Phase morphology often shows two glass transitions, corresponds to soft segment (soft segment) and rigid chain segment (hard section), wherein allusion quotation respectively
The representative of type such as polysulfones-dimethyl silicone polymer Alternating Block Copolymer, makrolon-dimethyl silicone polymer alternating block are total to
Polymers (CN103534297A) and polyimides-dimethyl silicone polymer Alternating Block Copolymer (CN103534316B).
Polyphenylene oxide (PPO) is a kind of excellent thermoplastic resin, is typically existed in copper/amine complex catalysis and oxygen
Under, by made from oxidative coupling.PPO has excellent resistance to high/low temperature performance, electricity as one of five large-engineering plastics
Insulating properties, chemical resistance, hydrolytic resistance, dimensional stability and creep resistance, therefore it is widely used in auto industry, electronics
Electrically, the multiple fields such as precision instruments, textile equipment.But since PPO molecule chain rigiditys are big, intermolecular force is strong,
There are melting temperature height, melt viscosity is big, processing and forming is difficult, impact resistance is poor, is also easy to produce the shortcomings of stress cracking, utilizes
PDMS is modified it always research hotspot, and is concentrated mainly on ABA type triblock copolymer preparation aspect.
CN1053203C discloses a kind of poly (arylene ether)-polysiloxane copolymer, it be by epoxy-functional poly (arylene ether) with
Amino or carboxy-functionalized polysiloxanes or the polysiloxanes and amino by epoxy-functional or carboxy-functionalized poly- Asia
Aryl ether is by the way that made from melt extrusion, the content of polysiloxanes is main below 20% in the ABA type triblock copolymer of gained
Syllabus is the physical property for improving polyphenylene oxide.
Basic industries global technology Co., Ltd of Saudi Arabia (New Chemical Materials, 2010,38 (4), 119-123) and
CN105315454A is to use the PDMS of phenol monomer and phenolic group sealing end as raw material, in copper/amine complex catalysis
Under, carry out by oxidative coupling polymerization reaction the preparations of PPO-PDMS triblock copolymers.
CN101717516B discloses a kind of preparation of polysiloxanes-polyphenylether segmented object for infiltration evaporation membrane material
OH, COOH or aminopropyl end group are introduced into polysiloxanes and polyphenylene oxide by method, then nitric acid or trifluoroacetic acid catalysis under into
Row reaction is made.This method there are it is apparent the defects of, it is well known that polysiloxanes be easy in the presence of strong acid occur strand
Fracture, degradation then reset and form cyclosiloxane, therefore the chain length of the structural regularity of gained copolymer and soft segment can be seriously inclined
From expection, it is bad to ultimately result in comprehensive performance.CN102161768A discloses a kind of dimethyl silicone polymer-polyphenylene oxide crosslinking
Block copolymer is prepared by tri- kinds of crosslinking agent, PPO and PDMS substance simultaneous reactions.Due to being that charging is anti-simultaneously
Should, PPO and PDMS can react alone with crosslinking agent and chain extension occur, it can therefore be concluded that the structural regularity of gained copolymer
Difference, and there are the PPO homopolymers of high molecular weight and PDMS homopolymers, it is difficult to it isolates and purifies.
Since the research of PPO is concentrated mainly on single end-cap product ω-phenolic hydroxyl group polyphenylene oxide, so the copolymerization with PDMS
Mainly ABA type triblock copolymer.In order to obtain good mechanical strength, ABA type triblock copolymer must have higher
Number-average molecular weight (usual more than 60,000), but this just seriously limits the relative amount of A, B component, because certain in copolymer
The length of segment is long, and it is more than necessary limit that can cause phase separation, as a result can seriously reduce the mechanical strength of material instead.And
(AB)nType block copolymer is then not limited, can be according to the relative amount of the component of two kinds of practical application request flexible modulation
With opposite chain length, thus with many performance advantages, but due to being limited be subject to PPO structures and copolymer synthesis process, grind
Study carefully long-term hysteresis.Further, since the oil resistant of PPO and PDMS, solvent resistance are poor, and pure PDMS segments are on -50 DEG C of left sides
Right to crystallize, this all largely limits the application range of copolymer.
The content of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of polyarylether-polysiloxane copolymer and its system
Preparation Method, obtained (AB)nType polyarylether-polysiloxane block copolymers, have good mechanical property, heat resistance and
Oil resistant, solvent resistance.
The present invention is introduced into phenyl substituent in the hard section of copolymer, fluorine silicon chain link is introduced in soft segment, to improve copolymerization
Heat resistance, resistance to low temperature, mechanical property and oil resistant, the solvent resistance of object, and existing synthetic technology route is carried out
Improve, pass through select hydrogen block polysiloxanes and efficient catalyst so that polysiloxanes both have higher reactivity,
Simultaneously again with good storage stability and the ripe simplicity of its preparation method, so that the preparation process of block copolymer
It is greatly easy, the control of alternating block structure is more accurate, stability greatly improves, thermoplastic silicone can be used as elastic
Body materials'use can also use as Noryl, also act as the works such as modified filler polyphenylene ether, makrolon, polysulfones
Engineering plastics carry out toughening and improve its processing performance, so as to be provided reliably in the popularization and application of association area for the material
Technology ensures.
The present invention is achieved by the following technical solutions：A kind of polyarylether-polysiloxane copolymer be based on polyarylether-
(AB) of polysiloxanesnType block copolymer has the structural formula as shown in following formula (I)：
Wherein, R is selected from one in the structural formula as shown in following formula (II)：
M, q separately natural numbers in 0~100, n, p separately natural number in 0~200,
And m, n, p with q differences when be zero；Natural numbers of the k in 1~20；Natural numbers of the x in 1~300, y are selected from 0~150
In natural number；Natural numbers of the z in 2~30.
The preparation method of the polyarylether-polysiloxane copolymer is with the polyarylether of phenolic hydroxyl group sealing end and hydrogen sealing end
Polysiloxanes for raw material, the Si -- H bond for making polysiloxane molecule chain end by catalyst activates so that two kinds together
Dehydrogenation polycondensation reaction occurs for polymers, is formed (AB) of compound with regular structurenType block copolymer, soft/hard section are by Si-O-Ph keys
It links together, specifically comprising following reaction step：
(1) dialkyl phenol, HO-R-OH, lauryl sodium sulfate (SDS) are added in reaction kettle with NaOH aqueous solutions and mixed
Conjunction forms mixed system, and stirring, which is warming up to 40~50 DEG C, dissolves solid matter, then adds potassium ferricyanide K3[Fe(CN)6]
And dimethylbenzene, 4~8h is stirred to react at 40~80 DEG C, then adds in NaCl until the amount of sediment is not further added by；So
It filters afterwards, collect sediment, washing, again with toluene or chloroform dissolving adjust pH value to 4~5, and reprecipitation is into methanol, washing
To neutrality, most after being dried under vacuum to constant weight at 80~120 DEG C to get α, ω-bisphenol hydroxy polyphenylene ether oligomer object (PPO-
2OH)。
The dialkyl phenol be selected from 2,6- xylenols (DMP), one kind in 2,6-diphenylphenol (DPP) or
Two kinds.
In the structural formula HO-R-OH, R is selected from one in the structural formula as shown in formula (II).
Wherein, the molar concentration of dialkyl phenol is mole of 0.02~0.06mol/L, dialkyl phenol and HO-R-OH
Than for 4~200: 1, K3[Fe(CN)6] with the molar ratio of dialkyl phenol it is 1~4: 1, lauryl sodium sulfate is in mixed system
In molar concentration for 0.001~0.004mol/L, the molar concentrations of NaOH aqueous solutions is 0.3~0.7mol/L, dimethylbenzene with
The volume ratio of NaOH aqueous solutions is 0~0.35: 1.
Preferably, the molar concentration of dialkyl phenol is 0.04~0.05mol/L, dialkyl phenol and HO-R-OH's
Molar ratio is 4~50: 1, K3[Fe(CN)6] with the molar ratio of dialkyl phenol it is 1.5~2.5: 1, lauryl sodium sulfate exists
Molar concentration in mixed system is 0.002~0.003mol/L, and the molar concentration of NaOH aqueous solutions is 0.45~0.55mol/
The volume ratio of L, dimethylbenzene and NaOH aqueous solutions is 0~0.2: 1.
Preferably, HCl/water solution is selected to adjust pH value.
(2) by 1,1,3,3- tetramethyl disiloxane (MMH), after cyclosiloxane and catalyst A mix in a kettle, in
4~8h is stirred to react at 50~70 DEG C, is subsequently cooled to room temperature, filter and (be suitable for solid catalyst) or is washed to is neutral (suitable
For liquid catalyst) catalyst is removed, it collects organic phase, 1~4h removing low boilings is kept under 160~200 DEG C/1 mmHg
Object is to get α, ω-dihydro polysiloxane oligomer (PS-2H)；
The cyclosiloxane is selected from 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane
(D3 F), hexamethyl cyclotrisiloxane (D3One or both of).
The one kind of the catalyst A in the concentrated sulfuric acid or storng-acid cation exchange resin.Preferably highly acid sun
Ion exchange resin.
Cyclosiloxane and MMHMolar ratio for 1~500: 1, the mass ratio of catalyst A and cyclosiloxane for 0.005~
0.2∶1.Preferably, cyclosiloxane and MMHMolar ratio for 1~160: 1, the mass ratio of catalyst A and cyclosiloxane is
0.01~0.08: 1.
(3) after mixing the product PPO-2OH, catalyst B and reaction dissolvent of step (1) in the reactor, in 20~120
Under DEG C stirring condition, 5~20 additions of the solution of the product PS-2H of step (2) or the product PS-2H of step (2) point add
Continue to be stirred to react 1~4h after entering；Room temperature is subsequently cooled to, is precipitated in methanol, collects solid product in 80~120 DEG C
Under be dried under vacuum to constant weight to get (AB)nType polyphenylene oxide-polysiloxane block copolymers.
The molar ratio of the catalyst B and product PPO-2OH of step (1) is 0.001~0.08: 1, is preferably 0.01
~0.02：1, wherein catalyst B are selected from triphenylphosphine radium chloride (RhCl (PPh3)3), three (dibenzalacetone) two palladium (Pd2
(dba)3), three (pentafluorophenyl group) borine (B (C6F5)3), three (perfluoronapthyl) borine (B (C10F7)3One or more of).Its
Middle B (C6F5)3(B (C10F7)3As strong Lewis acid, can fast activating Si -- H bond, but such catalyst be easy to cyanogen class,
The compound containing lone pair electrons such as esters, aldehydes, ketone, ethers, sulfone class forms complex inactivation, the B selected in the present invention
(C6F5)3(B (C10F7)3Catalyst can effectively carry out the preparation of copolymer, illustrate due to having in polyarylether molecule around ehter bond
There are larger steric hindrance, ehter bond and B (C6F5)3(B (C10F7)3It is difficult to form stable complex, so catalyst can keep high
Activity.
The mass ratio of the reaction dissolvent and the product PPO-2OH of step (1) are 5~100: 1, are preferably 30~50:
1；Wherein reaction dissolvent in toluene, dimethylbenzene, chloroform, chlorobenzene, dichloromethane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane one
Kind is several, is preferably toluene, chlorobenzene or its mixture.
When the product PS-2H of the step (2) feeds in the form of a solution, concentration of polymer solution is 2~50%, is preferably
20~40%；The solvent of solution is in toluene, dimethylbenzene, chloroform, chlorobenzene, dichloromethane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane
One or more, be preferably toluene, chlorobenzene or its mixture.
The molar ratio of the PS-2H of described step (2) the product and product PPO-2OH of step (1) is 0.4~2.1: 1,
Preferably 0.8~1.2: 1.
The copolyreaction temperature is preferably 60~90 DEG C.
The feeding interval is 5min~2h, is preferably 20~30min.
Polyarylether-polysiloxane copolymer in the present invention is the poly- silica with the polyarylether of phenolic hydroxyl group sealing end and hydrogen sealing end
Alkane is raw material, is prepared using catalytic dehydrogenation polycondensation reaction, when the mass fraction of silicone components in copolymer is more than
When 60%, product shows the property of thermoplastic silicone elastomers, and performance is close to silicon rubber, tensile strength and elongation at break
8MPa and more than 450% can be up to respectively simultaneously；When the mass fraction of silicone components is less than 30%, product shows to be modified
The property of polyphenylene oxide, performance is close to plastics.
Copolymer provided by the invention can be used as thermoplastic elastic material, with extend the species of organosilicon material and
Application field, the mechanical strength for improving organosilicon material, the physical and chemical performance and processing performance for improving polyphenylene oxide.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the present invention provides a kind of (AB)nType polyarylether-polysiloxane block copolymers, it can both have higher
Molecular weight, and can flexible modulation it is soft/relative amount and sequence length of hard section, it is embedding that ABA type three is better than on multinomial performance
Section copolymer.Phenyl substituent is introduced in hard section, temperature tolerance, mechanical property and the radiation resistance of copolymer can be improved, together
When in soft segment introduce fluorine silicon chain link, can effectively inhibit the crystallization of dimethyl siloxane segment in copolymer, so as to by its it is resistance to low
The warm limit extends to minimum -120 DEG C by -45 DEG C, while the introducing of fluoro-containing group can improve oil resistant, the solvent resistance of copolymer again
Energy；
(2) active end group of selected polysiloxanes is Si-H in the present invention, and the technology of preparing of hydrogen terminated polysiloxane is non-
Often ripe, preparation procedure simplicity (raw material commercialization, single step reaction), and the controllability of its molecular weight, experimental result
Reappearance and the storage stability of product be significantly better than polysiloxane oligomer in Noshay methods.Therefore, this is utilized
Block copolymer prepared by method in invention, PPO and polysiloxanes segment sequential structure is regular either in strand
The homogeneity of property or sequence length, is significantly better than that existing method, can reach stringent (AB)nType structure, so as to have
Effect ensures the stability of material property when prepared by the excellent properties of material and batch；
(3) preparation method of the invention have that reaction rate is fast, reaction condition is mild, product purity is high and simple purification,
The advantages that side reaction is few, by-product H2It is effusion system in the reaction, catalyst used is in the post-processing step of reaction
It is dissolved in precipitating reagent and being removed, avoid influence of the catalyst residual to material property；The preparation method of the present invention is not only applicable in
In (AB)nType block copolymer, but also it is suitable for ABA type triblock copolymer, the control of copolymer molecule structure is more smart
Really, the stability of product property also greatly improves, and reliable technology can be provided for the popularization and application of the material and is ensured.
Description of the drawings
Fig. 1 is the typical case of 12 target product of embodiment1H-NMR spectrum；
Fig. 2 is the typical GPC spectrograms of 12 target product of embodiment.
Specific embodiment
The present invention is described in further detail below by embodiment, raw materials used commercially available in embodiment or use
It is prepared by conventional method.
First, the preparation of α, ω-bisphenol hydroxy polyphenylene ether oligomer object PPO-2OH
Implementation steps 1a
One equipped with thermometer, in churned mechanically 2L three-necked flasks, by 0.04mol 2,6- xylenols (DMP),
0.004mol 2,2- double (4- hydroxyls -3,5- 3,5-dimethylphenyl) propane (bisphenol-A), 0.002 mol dodecyl sulphates
The NaOH aqueous solutions of sodium (SDS) and 1L 0.5mol/l are added in reaction kettle and mixed, and are stirred, are warming up to 50 DEG C and make solid matter molten
Solution, then adds 0.09mol potassium ferricyanides K3[Fe(CN)6], reaction 6h is vigorously stirred at 50 DEG C.NaCl is added in until precipitation
It until the amount of object is not further added by, is cooled to room temperature, then filters, collects sediment, washing, then HCl is added in after being dissolved with chloroform
Aqueous solution adjusts pH value to 4~5, is then precipitated in methanol, is washed to neutrality, most after being dried under vacuum to constant weight at 80 DEG C,
Up to PPO-2OH, yield 93.6%.Its MnIt is 5600 through gel permeation chromatography (GPC) test, polydispersity index PDI is 1.96
(leacheate is toluene, standard specimen is polystyrene).
Implementation steps 1b
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " replace with " 0.01mol bisphenol-As ", potassium ferricyanide K3[Fe(CN)6] amount be changed to 0.1mol, other preparation conditions are constant.
Product yield 92.2%, Mn：2800, PDI：1.79.
Implementation steps 1c
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " " 0.006mol bisphenol-As " is replaced with, other preparation conditions are constant.Product yield 91.7%, Mn：3500, PDI：1.87.
Implementation steps 1d
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " " 0.003mol 3,5,3 ', 5 '-tetramethyl -4,4 '-dihydroxybiphenyl " is replaced with, other preparation conditions are constant.Product
Yield 95.5%, Mn：4400, PDI：1.99.
Implementation steps 1e
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " " 0.0015mol 4,4 '-diphenyl methylene bis-phenol (bisphenol b P) " is replaced with, other preparation conditions are constant.Product yield
93.0%, Mn：8300, PDI：1.77.
Implementation steps 1f
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " it replaces with " 0.001mol 4,4 '-dihydroxy diphenyl ether ", the amount of SDS is changed to 0.004mol, and other preparation conditions are not
Become.Product yield 94.1%, Mn：14000, PDI：1.86.
Implementation steps 1g
By " double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (tetramethyls pair of 0.004mol 2,2- in implementation steps 1a
Phenol A) " it replaces with " 0.001mol 4,4 '-dihydroxybiphenyl ", the amount of SDS is changed to 0.004mol, and adds in 200ml chloroforms,
Other preparation conditions are constant.Product yield 92.8%, Mn：34000, PDI：1.95.
Implementation steps 1h
One equipped with thermometer, in churned mechanically 2L three-necked flasks, by 0.04mol 2,6-diphenylphenols (DPP),
0.002mol 2,2- be double-(4- hydroxyls -3,5- 3,5-dimethylphenyl) hexafluoropropane (bisphenol-A F), 0.004mol SDS,
The NaOH aqueous solutions and 150mL dimethylbenzene of 1L 0.5mol/l are added in reaction kettle and mixed, and are stirred, are warming up to 50 DEG C and make solids
Matter dissolves, and then adds 0.1mol potassium ferricyanides K3[Fe(CN)6], reaction 7h is vigorously stirred at 70 DEG C.Add in NaCl until
It until the amount of sediment is not further added by, is cooled to room temperature, adds 500ml methanol, be then decanted, filter, collect sediment, water
It washes, then HCl/water solution is added in after being dissolved with chloroform and adjusts pH value to 4~5, be then precipitated in methanol, be washed to neutrality, finally
Constant weight is dried under vacuum at 120 DEG C to get PPO-2OH.Product yield 91.4%, Mn：11800, PDI： 2.04.
Implementation steps 1i
By " 0.002mol 2,2- pairs-(4- hydroxyls -3,5- 3,5-dimethylphenyl) hexafluoropropane (tetramethyl in implementation steps 1h
Base bisphenol AF) " " 0.004mol 4,4 '-(1- phenethyls) bis-phenol (bisphenol-ap) " is replaced with, other preparation conditions are constant.Product
Yield 92.9%, Mn：7800, PDI：2.04.
Implementation steps 1j
By " 0.002mol 2,2- pairs-(4- hydroxyls -3,5- 3,5-dimethylphenyl) hexafluoropropane (tetramethyl in implementation steps 1h
Base bisphenol AF) " it replaces with " 0.001mol bisphenol-As ", reaction temperature is 80 DEG C, and other preparation conditions are constant.Product is received
Rate 90.7%, Mn：27000, PDI：2.13.
Implementation steps 1k
" 0.04mol DPP " in implementation steps 1h is replaced with into " 0.02mol DMP and 0.02mol DPP ",
" 0.002mol 2,2- pairs-(4- hydroxyls -3,5- 3,5-dimethylphenyl) hexafluoropropane (bisphenol-A F) " replace with
" double (4- hydroxyls -3, the 5- 3,5-dimethylphenyl) propane (bisphenol-A) of 0.002mol 2,2- ", other preparation conditions are constant.Production
Object yield 92.3%, Mn：8200, PDI：2.01.
Implementation steps 1l
" 0.04mol DPP " in implementation steps 1h is replaced with into " 0.01mol DMP and 0.03mol DPP ", other systems
Standby condition is constant.Product yield 93.8%, Mn：9500, PDI：2.11.
Implementation steps 1m
" 0.04mol DPP " in implementation steps 1h is replaced with into " 0.03mol DMP and 0.01mol DPP ", other systems
Standby condition is constant.Product yield 91.5%, Mn：6900, PDI：1.94.
2nd, the preparation of α, ω-dihydro polysiloxane oligomer PS-2H
Implementation steps 2a
In the 500mL three-necked flasks equipped with thermometer, mechanical agitation and reflux condensing tube, 20g highly acids sun is added in
Then ion exchange resin is adding in 1mol D as catalyst A3With 0.3mol MMH, 6h is stirred to react at 60 DEG C, is cooled down
Afterwards by reaction mixture Filtration of catalyst A, low-boiling-point substance most is removed to get colourless after holding 2h under 160 DEG C/1 mmHg
Bright PS-2H.Yield：85.0%, Mn：780, PDI：1.87 (leacheate is tetrahydrofuran, standard specimen PDMS).
Implementation steps 2b
With reference to implementation steps 2a, MMHQuantitative change more 0.11mol MMH, it is other to remain unchanged.Yield：84.2%, Mn：
2200, PDI：1.92.
Implementation steps 2c
With reference to implementation steps 2a, MMHQuantitative change more 0.044mol MMH, it is other to remain unchanged.Yield：85.5%, Mn：
5600, PDI：1.82.
Implementation steps 2d
With reference to implementation steps 2a, MMHQuantitative change more 0.033mol MMH, it is other to remain unchanged.Yield：86.7%, Mn：
7700, PDI：1.88.
Implementation steps 2e
In the 500mL three-necked flasks equipped with thermometer, mechanical agitation and reflux condensing tube, 1mol D are added in3、
0.022mol MMHWith the concentrated sulfuric acid of 3g 98%, 5h is stirred to react at 60 DEG C, reaction mixture is transferred to liquid separation after cooling
In funnel, divide to fall lower water phase, organic phase with water is extracted repeatedly, is washed till neutrality, most taken off after holding 2h under 180 DEG C/1mmHg
Except low-boiling-point substance is to get the PS-2H of water white transparency.Yield：81.4%, Mn：11000, PDI：1.97.
Implementation steps 2f
With reference to implementation steps 2e, MMHQuantitative change more 0.011mol MMH, it is other to remain unchanged.Yield：83.4%, Mn：
22300, PDI：1.85.
Implementation steps 2g
In the 500mL three-necked flasks equipped with thermometer, mechanical agitation and reflux condensing tube, 0.85 mol D are added in3、
0.15mol D3F、0.022mol MMHWith the concentrated sulfuric acid of 4g 98%, 4h is stirred to react at 50 DEG C, mixes reaction after cooling
Object is transferred in separatory funnel, point fall lower water phase, organic phase with water is extracted repeatedly, is washed till neutrality, most after 200 DEG C/
PS-2H of the 2h removing low-boiling-point substances to get water white transparency is kept under 1mmHg.Yield：82.5%, Mn：12200, PDI：2.08.
Implementation steps 2h
With reference to implementation steps 2g, cyclosiloxane is changed to 0.7mol D3With 0.3mol D3F, it is other to remain unchanged.Yield：
81.6%, Mn：14300, PDI：2.13.
Implementation steps 2i
With reference to implementation steps 2g, cyclosiloxane is changed to 0.6mol D3With 0.4mol D3F, it is other to remain unchanged.Yield：
81.0%, Mn：15500, PDI：2.25.
Implementation steps 2j
With reference to implementation steps 2g, cyclosiloxane is changed to 0.4mol D3With 0.6mol D3F, it is other to remain unchanged.Yield：
80.5%, Mn：18100, PDI：2.32.
Implementation steps 2k
With reference to implementation steps 2g, cyclosiloxane is changed to 0.3mol D3With 0.7mol D3F, it is other to remain unchanged.Yield：
78.4%, Mn：19000, PDI：2.37.
Implementation steps 2l
With reference to implementation steps 2g, cyclosiloxane is changed to 0.15mol D3With 0.85mol D3F, it is other to remain unchanged.It receives
Rate：77.0%, Mn：20600, PDI：2.30.
Implementation steps 2m
With reference to implementation steps 2g, cyclosiloxane is changed to 0.6mol D3With 0.4mol D3F, MMHQuantitative change more
0.033mol MMH, it is other to remain unchanged.Yield：80.3%, Mn：10400, PDI：2.21.
Implementation steps 2n
With reference to implementation steps 2g, cyclosiloxane is changed to 0.6mol D3With 0.4mol D3F, MMHQuantitative change more
0.044mol MMH, it is other to remain unchanged.Yield：81.2%, Mn：8200, PDI：2.24.
Implementation steps 2o
With reference to implementation steps 2g, cyclosiloxane is changed to 0.6mol D3With 0.4mol D3F, MMHQuantitative change more
0.066mol MMH, it is other to remain unchanged.Yield：81.7%, Mn：5100, PDI：2.19.
Implementation steps 2p
With reference to implementation steps 2g, cyclosiloxane is changed to 1mol D3F, it is other to remain unchanged.Yield：77.8%, Mn：
19600, PDI：2.24.
3rd, the preparation of polyphenylene ether-poly silicone block copolymer
Number in PPO-2OH and PS-2H brackets in following embodiment is the above-mentioned implementation steps institute accordingly numbered
The product obtained.GPC tests leacheate is toluene in embodiment, standard specimen is polystyrene.
Embodiment 1
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 5600
PPO-2OH(1a)5.6g(1mmol)、B(C6F5)356mg, chlorobenzene 300mL are stirred, are warming up to 70 DEG C.In constant pressure funnel
Add in MnFor 11000 PS-2H (2e) 11g (1mmol), 12 times (per minor tick 0.5h, every time about 1mL) is then divided to be added dropwise to burning
In bottle.With the progress of reaction, it can be observed there is bubble slowly to be escaped from solution, reaction system viscosity becomes larger.It is added dropwise
After the reaction was continued 3h, reaction system viscosity increases without apparent, also escaped without gas, stop reaction, be cooled to room temperature, will
Reaction mixture is precipitated in 1000mL methanol, filters out white rubber shape product, constant weight, gained are dried under vacuum at 80 DEG C
(AB)nThe yield of type polyarylether-polysiloxane copolymer is 97.5%, MnFor 93300, PDI 3.14.
Embodiment 2
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 4400
PPO-2OH(1d)4.4g(1mmol)、B(C6F5)322mg, chlorobenzene 265mL are stirred, are warming up to 80 DEG C.In constant pressure funnel
Add in MnFor 7700 PS-2H (2d) 7.7g (1mmol), 5 times (per minor tick 1h, every time about 1.5mL) is then divided to be added dropwise to burning
In bottle.With the progress of reaction, it can be observed there is bubble slowly to be escaped from solution, reaction system viscosity becomes larger.It is added dropwise
After the reaction was continued 4h, reaction system viscosity increases without apparent, also escaped without gas, stop reaction, be cooled to room temperature, will
Reaction mixture is precipitated in 1000mL methanol, filters out white chunks product, and constant weight is dried under vacuum at 100 DEG C.Gained
(AB)nThe yield 98.2% of type polyarylether-polysiloxane copolymer, Mn：115400, PDI：3.26.
Embodiment 3
In the 1L four-hole boiling flasks equipped with thermometer, reflux condensing tube, mechanical agitation and constant pressure funnel, M is added inn
For 8300 PPO-2OH (1e) 8.3g (1mmol), B (C6F5)317mg, chlorobenzene 232mL are stirred, are warming up to 120 DEG C.In constant pressure
M is added in dropping funelnFor 19000 PS-2H (2k) 19g (1mmol), then divide 20 times (per minor tick 20min, every time about
1mL) it is added dropwise in flask.The reaction was continued after being added dropwise 1h, then stops reaction, is cooled to room temperature, reaction mixture is sunk
It forms sediment into 1000 mL methanol, filters out white rubber shape product, constant weight is dried under vacuum at 120 DEG C.(AB) of gainednType
The yield 98.2% of polyarylether-polysiloxane copolymer, Mn：168800, PDI：3.45.
Embodiment 4
In the 1L four-hole boiling flasks equipped with thermometer, reflux condensing tube, mechanical agitation and constant pressure funnel, M is added inn
For 14000 PPO-2OH (1f) 14g (1mmol), B (C6F5)314mg, chloroform 200mL are stirred, are warming up to 60 DEG C.It is dripped in constant pressure
M is added in liquid funnelnFor 780 PS-2H (2a) 1.2g (1.5 mmol), then divide 12 times (per minor tick 1h, every time about
0.1mL) it is added dropwise in flask.The reaction was continued after being added dropwise 2h, then stops reaction, is cooled to room temperature, by reaction mixture
It is precipitated in 1000mL methanol, filters out white chunks product, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType gathers
The yield 97.9% of aryl oxide-polysiloxane copolymer, Mn：123100, PDI：3.13.
Embodiment 5
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 9500
PPO-2OH(11)9.5g(1mmol)、B(C10F7)30.475g, dichloromethane 500mL, stirring, 20 DEG C of maintenance system temperature.
M is added in constant pressure funnelnFor 22300 PS-2H (2f) 17.9g (0.8mmol), then divide 20 times (per minor tick 2h,
Each about 1.1mL) it is added dropwise in flask.The reaction was continued after being added dropwise 3h, then stops reaction, is cooled to room temperature, will react
Mixture precipitation filters out white rubber shape product, constant weight is dried under vacuum at 90 DEG C into 1000 mL methanol.Gained
(AB)nThe yield 96.3% of type polyarylether-polysiloxane copolymer, Mn：186200, PDI：3.48.
Embodiment 6
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 11800
PPO-2OH(1h)11.8g(1mmol)、B(C10F7)30.472g, toluene 300mL are stirred, are warming up to 40 DEG C.It is leaked in constant pressure addition
M is added in bucketnFor 14300 PS-2H (2h) 14.3g (1 mmol), then divide 15 (per minor tick 1h, every time about 1mL) drops
It adds in flask.The reaction was continued after being added dropwise 3h, then stops reaction, is cooled to room temperature, reaction mixture is precipitated to
In 1000mL methanol, white chunks product is filtered out, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType polyarylether-poly-
The yield 97.0% of silicone copolymers, Mn：177300, PDI：3.39.
Embodiment 7
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 8200
PPO-2OH(1k)8.2g(1mmol)、B(C10F7)30.164g, dimethylbenzene 150mL are stirred, are warming up to 90 DEG C.In constant pressure addition
M is added in funnelnFor 5100 PS-2H (2o) 6.0g (1.17 mmol), then divide 12 times (per minor tick 45min, every time about
0.5mL) it is added dropwise in flask.The reaction was continued after being added dropwise 2h, then stops reaction, is cooled to room temperature, by reaction mixture
It is precipitated in 1000mL methanol, filters out white chunks product, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType gathers
The yield 96.5% of aryl oxide-polysiloxane copolymer, Mn：76500, PDI：3.12.
Embodiment 8
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 6900
PPO-2OH(1m)6.9g(1mmol)、RhCl(PPh3)369mg, tetrahydrofuran 200mL are stirred, are warming up to 40 DEG C.It is dripped in constant pressure
M is added in liquid funnelnFor 12200 PS-2H (2g) 14.6g (1.2mmol), then divide 15 times (per minor tick 1.5h, every time
About 1mL) it is added dropwise in flask.The reaction was continued after being added dropwise 3h, then stops reaction, is cooled to room temperature, by reaction mixture
It is precipitated in 1000 mL methanol, filters out white rubber shape product, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType
The yield 94.1% of polyarylether-polysiloxane copolymer, Mn：84800, PDI：3.29.
Embodiment 9
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 7800
PPO-2OH(1i)7.8g(1mmol)、Pd2(dba)362.4mg, Isosorbide-5-Nitrae-dioxane 220mL are stirred, are warming up to 60 DEG C.In perseverance
M is added in pressure dropping funelnFor 5600 PS-2H (2c) 6.72g (1.2 mmol), then divide 13 times (per minor tick 1h, every time
About 0.5mL) it is added dropwise in flask.The reaction was continued after being added dropwise 2h, then stops reaction, is cooled to room temperature, will reaction mixing
Object is precipitated in 1000mL methanol, filters out white chunks product, and constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType
The yield 94.7% of polyarylether-polysiloxane copolymer, Mn：107800, PDI：3.44.
Embodiment 10
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 34000
PPO-2OH(1g)34g(1mmol)、B(C6F5)368mg, chlorobenzene 300mL are stirred, are warming up to 70 DEG C.In constant pressure funnel
Add in MnFor 19000 PS-2H (2k) 7.6g (0.4mmol), 10 times (per minor tick 1.5h, every time about 1mL) is then divided to be added dropwise
Into flask.The reaction was continued after being added dropwise 3h, then stops reaction, is cooled to room temperature, reaction mixture is precipitated to
In 1200mL methanol, white chunks product is filtered out, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType polyarylether-poly-
The yield 97.5% of silicone copolymers, Mn：96300, PDI：2.87.
Embodiment 11
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 6900
PPO-2OH(1m)6.9g(1mmol)、RhCl(PPh3)369mg, tetrahydrofuran 150mL are stirred, are warming up to 60 DEG C.It is dripped in constant pressure
M is added in liquid funnelnFor 19600 PS-2H (2p) 15.7g (0.8mmol) and 50ml tetrahydrofurans, then divide 20 times (every time
30min is spaced, every time about 3mL) it is added dropwise in flask.The reaction was continued after being added dropwise 2h, then stops reaction, is cooled to room
Reaction mixture is precipitated in 800mL methanol by temperature, filters out white rubber shape product, constant weight is dried under vacuum at 80 DEG C.
(AB) of gainednThe yield 95.8% of type polyarylether-polysiloxane copolymer, Mn：197400, PDI： 2.79.
Embodiment 12
In the 1L three-necked flasks equipped with thermometer, mechanical agitation and constant pressure funnel, M is added innFor 8200
PPO-2OH(1k)8.2g(1mmol)、B(C6F5)30.016g, chlorobenzene 240mL are stirred, are warming up to 80 DEG C.In constant pressure funnel
Middle addition MnFor 18100 PS-2H (2j) 19.9g (1.1mmol), then divide 20 times (per minor tick 30min, every time about 1mL)
It is added dropwise in flask.The reaction was continued after being added dropwise 2h, then stops reaction, is cooled to room temperature, reaction mixture is precipitated to
In 1000mL methanol, white chunks product is filtered out, constant weight is dried under vacuum at 80 DEG C.(AB) of gainednType polyarylether-poly-
The yield 94.9% of silicone copolymers, Mn：187600, PDI：3.28.Product1H-NMR spectrum and GPC spectrograms are shown in attached respectively
Fig. 1 and attached drawing 2.
Above example is not limiting the scope of the invention, can also there are many operative combination, this field
Those of ordinary skill can be exported directly to all situations from following examples, should all be protection scope of the present invention.
Claims (10)
1. a kind of polyarylether-polysiloxane copolymer, which is characterized in that a kind of polyarylether-polysiloxane copolymer is
(AB) based on polyarylether-polysiloxanesnType block copolymer has the structural formula as shown in following formula (I)：
Wherein, R is selected from one in the structural formula as shown in following formula (II)：
M, q separately natural numbers in 0~100, n, p separately natural number in 0~200, and m,
N, p and q cannot be zero simultaneously；Natural numbers of the k in 1~20；Natural numbers of the x in 1~300, y is in 0~150
Natural number；Natural numbers of the z in 2~30.
2. a kind of preparation method of polyarylether-polysiloxane copolymer as described in claim 1, which is characterized in that described
Preparation method is catalytic dehydrogenation condensation methods, specifically comprising following reaction step：
(1) by dialkyl phenol, HO-R-OH, lauryl sodium sulfate and NaOH aqueous solutions add in reaction kettle in be mixed to form
Mixed system, stirring are warming up to 40~50 DEG C and dissolve solid matter, then add the potassium ferricyanide and dimethylbenzene, 40~80 DEG C
Under be stirred to react 4~8h, then add in NaCl until the amount of sediment is not further added by until, then filtering, collection sediment, water
It washes, again with toluene or chloroform dissolving adjust pH value to 4~5, are then precipitated in methanol, are washed to neutrality, most after 80~
Constant weight is dried under vacuum at 120 DEG C to get α, ω-bisphenol hydroxy polyphenylene ether oligomer object；
(2) after mixing 1,1,3,3- tetramethyl disiloxane, cyclosiloxane and catalyst A in a kettle, in 50~70 DEG C
Under be stirred to react 4~8h, be subsequently cooled to room temperature, filter or be washed to it is neutral remove catalyst, collect organic phase, in 160~
1~4h is kept to remove low-boiling-point substance to get α, ω-dihydro polysiloxane oligomer under 200 DEG C/1mmHg；
(3) after mixing the product of step (1), catalyst B and reaction dissolvent in the reactor, in 20~120 DEG C of stirring conditions
Under, 5~20 additions of the product of step (2) point continue to be stirred to react 1~4h after addition；Room temperature is subsequently cooled to, is sunk
It forms sediment into methanol, collects solid product and constant weight is dried under vacuum at 80~120 DEG C to get (AB)nType polyphenylene ether-poly siloxanes
Block copolymer.
A kind of 3. preparation method of polyarylether-polysiloxane copolymer according to claim 2, which is characterized in that step
(1) dialkyl phenol one or two in 2,6- xylenols, 2,6-diphenylphenol in, wherein dialkyl phenol
Molar concentration is 0.02~0.06mol/l.
4. the preparation method of a kind of polyarylether-polysiloxane copolymer according to Claims 2 or 3, which is characterized in that two
The molar ratio of hydrocarbylphenol and HO-R-OH are 4~200: 1, and the molar ratio of the potassium ferricyanide and dialkyl phenol is 1~4: 1,12
Molar concentration of the sodium alkyl sulfate in mixed system is 0.001~0.004mol/L, and the molar concentration of NaOH aqueous solutions is 0.3
The volume ratio of~0.7mol/L, dimethylbenzene and NaOH aqueous solutions is 0~0.35: 1.
A kind of 5. preparation method of polyarylether-polysiloxane copolymer according to claim 2, which is characterized in that step
(2) cyclosiloxane is selected from 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane, three silicon of pregnancy basic ring in
One or both of oxygen alkane.
A kind of 6. preparation method of polyarylether-polysiloxane copolymer according to claim 2 or 5, which is characterized in that ring
Siloxanes and 1, the molar ratio of 1,3,3- tetramethyl disiloxane is 1~500: 1, and the mass ratio of catalyst A and cyclosiloxane is
0.005~0.2: 1, catalyst A are selected from the concentrated sulfuric acid or storng-acid cation exchange resin.
A kind of 7. preparation method of polyarylether-polysiloxane copolymer according to claim 2, which is characterized in that step
(3) molar ratio of catalyst B and step (1) product described in are 0.001~0.08: 1, and wherein catalyst B is selected from triphenyl
One kind or several in phosphine radium chloride, three (dibenzalacetone) two palladium, three (pentafluorophenyl group) borines, three (perfluoronapthyl) borines
Kind.
A kind of 8. preparation method of polyarylether-polysiloxane copolymer according to claim 2, which is characterized in that step
(3) mass ratio of reaction dissolvent and step (1) product described in is 5~100: 1, and wherein reaction dissolvent is selected from toluene, diformazan
One or more of benzene, chloroform, chlorobenzene, dichloromethane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane.
A kind of 9. preparation method of polyarylether-polysiloxane copolymer according to claim 2, which is characterized in that step
(3) when the step of described in (2) product feeds in the form of a solution, concentration of polymer solution is 2~50%, and the solvent of solution is selected from first
One or more of benzene, dimethylbenzene, chloroform, chlorobenzene, dichloromethane, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane.
10. a kind of preparation method of polyarylether-polysiloxane copolymer according to claim 2 or 9, which is characterized in that
The step of described in step (3) (2) product and the molar ratio of step (1) product be 0.4~2.1: 1.
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