CN106565951B - Poly- (2,6 dimethyl phenylate) oligomer of phosphorus system and preparation method thereof and thermosetting compound - Google Patents
Poly- (2,6 dimethyl phenylate) oligomer of phosphorus system and preparation method thereof and thermosetting compound Download PDFInfo
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Abstract
The present disclosure generally relates to poly- (2,6 dimethyl phenylate) oligomers of phosphorus system and preparation method thereof and thermosetting compound.Wherein, poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system of the present invention containing unsaturated group can be further used for preparing fire retardant thermosetting compound, and the thermosetting compound has anti-flammability, low-k, low dielectric absorption and high glass transition temperature.
Description
Technical field
The present disclosure generally relates to poly- (the 2,6 dimethyl phenylate) oligomer of phosphorus system and preparation methods.Wherein, the present invention contains insatiable hunger
It can further harden with the double bond phosphorus system of base poly- (2,6 dimethyl phenylate) oligomer to prepare fire retardant thermosetting compound, the heat
Solidfied material has anti-flammability, low-k, low dielectric absorption and high glass transition temperature.
Background technique
With the progress of semiconductor technology, the size of component also constantly reduces, and enters in micron field, then simple layer
Conducting wire is not applied and is used, it is necessary to develops towards three-dimensional space, thus it is online in necessary construction multiple layer metal, just it is able to satisfy development
Demand.It is main to will affect its efficiency there are two problem in the inline mechanism journey of multiple layer metal: one, to be plain conductor and dielectric
Signal propagation delays caused by matter layer (RC delay)；Two, the signal between plain conductor interferes (cross talk), separately
The speed and dielectric constant square of outer signal transmitting are inversely proportional proportional with dielectric absorption, therefore develop dielectric materials and are
Project important now.
Poly- (2,6 benzyl ether) (poly (2,6-dimethyl-1,4-phenylene oxide) or abbreviation PPO) is one
Kind engineering plastics, the thermoplasticity developed in 1956 by the A.S.Hay of unusual (General Electric) company of the U.S.
Macromolecule [1].PPO structure is firm, and cause makes it have high glass transition temperature (about 210 DEG C of Tg), high-tensile, rigid, resistance to
Impact strength, creep resistance and low-expansion coefficient (CTE:2.9 × 10-5In/ ℉, -20 ℉~150 ℉) etc. characteristics, remove this,
PPO has good resistance to solvent, acidproof, alkaline-resisting, and low water absorption.Macromolecule is often formed in the method for injection, and PPO
With low molding shrinkage.In terms of electrical characteristic, PPO has low-k.
For the requirement for reaching high-performance and high dimensional stability, copper clad laminate resin needs to seek thermosetting property.But for fear of PPO sheet
Body structure relationship limits PPO and develops and apply, scholar Ueda et al. [2] in substrate so that self-crosslinking hardens having any problem property
With oxidative coupling by 2,6- xylenol (2,6-Dimethylphenol) and 2- allyl -6- cresols (2-Allyl-
It 6-methylphenol) is copolymerized, obtains PPO, the PPO after modification that side chain has allyl, itself can become thermosetting property high score
Son still has high Tg and low dielectric constant after modified PPO hardening.So, since PPO has high molecular weight, make
It is with quite high stickiness, and solubility is bad, bad to the impregnation of glass fibre, and limits its answering in copper clad laminate
With.
2006, Ishii et al. synthesized distant chela PPE giant molecule monomer (the telechelic PPE of low molecular weight
Macromonomers, PPE-M), and the phenol terminal groups of the giant molecule monomer and 4- 1-chloro-4-methyl-benzene are reacted,
And the PPO compound of styrene end is arrived, vinyl phenyl PPE giant molecule monomer (VB-PPE-M) institute of structure such as formula (1)
Show [3].PPE-M and epoxy resin and cyanate are copolymerized by Peters in 2007 et al., keep the performance of its thermosetting compound big
Width promotes [4].2011, Peters et al. [5] by commodity PPE-M under SABIC house flag (orSA90 end)
Phenolic group is modified, and so that its end is had unsaturated double-bond structure, as shown in formula (1).Contain methacrylic acid when importing PPE-M
When ester (methacrylate) terminal groups, the methylpropenyl PPE giant molecule monomer (M-PPO-M) of structural formula such as formula (1),
Its trade name NORYLTMResin SA 9000。
Due to the development of printed circuit board now, for the electrical properties, thermal property and flame retardancy etc. of high frequency substrate
Requirement it is very high, especially must reach V-0 grade, therefore the space that material still makes progress in this regard in the fire retardant test of UL-94,
PPO can be made to meet the demand of market today, increase its application value.However, PPO has flammability, electron level can not be reached
The requirement of product UL-94V-0.In recent years, organic phosphorus compound has been studied for high molecular polymer with preferred resistance to
Characteristic is fired, and compared to flame retardant containing halogen, organic phosphorus compound is that solid phase is fire-retardant, less likely generates smog and has poison gas
Body.Known addition type flame retardant, other than it can reduce the engineering properties of material, as the migration of flame retardant molecule or
Volatilize and cause the decline of its resistance to fuel efficiency fruit.In early stage research, the additional incombustible agent that adds makes it possible to reach preferred difficulty
Fuel efficiency fruit.Such as scholar Leu et al. [6] is added in PPO using nitrogenous phosphorus flame retardant, because the nitrogen phosphorus of fire retardant multiplies effect altogether
It answers, is allowed to UL-94 and reaches V-0 grade.In addition in PPO and polystyrene (PS) blending system, though the impact resistance of enhancing PPO is strong
Degree, but the case where fire retardant aspect is downslide, incombustible agent need to be added, again to reach preferred fire retardant effect, therefore scholar
Takeda et al. [7] utilizes different phosphorous aromatic series incombustible agents, inquires into the fire retardant effect to PPO/PS.It was found that the phosphorous difficulty of addition
Agent is fired, the self-extinguishing time of burning can be effectively reduced, promote its flame resistance.In addition, woods et al. disclosed a series of phosphorus in 2014
It is derivative, is with the miscellaneous -10- phosphorus phenanthrene -10- oxide (9,10-dihydro-9-oxa-10- of 9,10- dihydro-9-oxy
Phosphaphenanthrene10-oxide, hereinafter referred to as DOPO), the phosphorus group for having fire-retardant is introduced directly into the structure of PPO,
To replace additional addition incombustible agent [8].Its result reaches VTM-0 grade in UL-94 when phosphorus content is 1%, and display is by containing
The importing of phosphorus group can effectively promote its flame retardancy really.
Bibliography:
1.Hay,A.S.J.Polym Sci Part A:Polym Chem 1998,36,505.
2.Fukuhara,T.；Shibasaki,Y.；Ando,S.；Ueda,M.Polymer 2004,45,843
3.US 6,995,195B2
4.E.N.Peters,A.K.,E.Delsman,H.Guo,A.Carrillo,G.Rocha In Society of
Plastics Engineers Annual Technical Conference(ANTEC 2007):Plastics
Encounter,Cincinnati,Ohio.,6-11May,2007；Curran Associates,Inc.；pp 2125-2128.
5.S.Fisher,H.G.,M.Jeevanath,E.Peters,SABIC Innovative Plastics In
Polyphenylene Ether Macromonomer:X.Vinyl Terminated Telechelic Macromers,69th
Annual Technical Conference of the Society of Plastics Engineers 2011(ANTEC
2011),Boston,Massachusetts,USA,1-5May,2011；pp 2819-2822.
6.Leu,T.S.；Wang,C.S.J Appl Polym Sci 2004,92,410
7.Kunihiko,T.；Fumiko,A.；Masao,K.；Shigeki,T.J Appl Polym Sci 1997,64,
1175.
8.Lin,C.H.,Tsai,Y.J.,Shih,Y.S.,Chang,H.C.Polym Degradation and
Stability2014,99,105
Summary of the invention
The present disclosure generally relates to poly- (2, the 6 dimethyl phenylate) oligomers of phosphorus system, specifically, the present invention includes two kinds of aspects,
Phosphorus group is imported into PPO first, obtains poly- (2,6 dimethyl benzenes of the bis-phenol oligomer with phosphorus group, especially phosphorus system
Ether) bis-phenol oligomer.Then poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system obtained is modified again, imports three kinds
Poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group is further made in unsaturated double-bond.Such as phosphorus system is gathered
(2,6 dimethyl phenylate) bis-phenol oligomer reacts to obtain the phosphorus system PPO of styrol with 4- 1-chloro-4-methyl-benzene, due to styrene
Group is low polarity and hydrophobic structure, will have low-k and low dielectric absorption, has the low dielectric of flame retardancy to obtain
Thermosetting compound.
Poly- (the 2,6 dimethyl phenylate) oligomer of phosphorus system
Therefore, poly- (2, the 6 dimethyl phenylate) oligomer of phosphorus system of the invention, it includes the structures of such as following formula (2):
Wherein group out of the ordinary has following meanings:
P1Expression be not present or
P2It indicates
R1、R2、R3Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
R4Indicate H or the alkenyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or combinations thereof, preferably
M, n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system
In above-mentioned poly- (2, the 6 dimethyl phenylate) oligomer of phosphorus system of the present invention, wherein working as R4When for H, formula (2) is poly- for phosphorus system
(2,6 dimethyl phenylate) bis-phenol oligomer, and an at least formula (2) oligomer system is indicated with the oligomer of such as formula (3):
Wherein group out of the ordinary has following meanings:
P1Expression be not present or
P2It indicates
R1、R2、R3Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
M, n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Specifically, an at least formula (3) oligomer system is indicated with the oligomer of such as formula (IIa) or formula (IIc):
Wherein group out of the ordinary has following meanings:
R1、R2、R3Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
M, n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Specifically, formula (IIa) is preferred are as follows:
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
Specifically, formula (IIc) is preferred are as follows:
Wherein, R1For H, CH3Or C2H5、R2For H or CH3And R3 is H or CH3；Or
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
Poly- (the 2,6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group
In above-mentioned poly- (2, the 6 dimethyl phenylate) oligomer of phosphorus system of the present invention, wherein working as R4When not being H, formula (2) is containing not
It is saturated poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system of base, a wherein at least formula (2) oligomer system is with the widow of such as formula (4)
Polymers indicates:
Wherein group out of the ordinary has following meanings:
P1Expression be not present or
P2It indicates
R1、R2、R3Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
R’4When the alkenyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or combinations thereof, preferably
M, n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Specifically, a wherein at least formula (4) oligomer system is indicated with the oligomer of such as formula (IIIa) or formula (IIIc):
Wherein group out of the ordinary has following meanings:
R1、R2、R3Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
R4Indicate H or the alkenyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or combinations thereof, preferably
M, n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Specifically, formula (IIIa) is preferred are as follows:
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
Specifically, formula (IIIc) is preferred are as follows:
Wherein, R1For H, CH3Or C2H5、R2For H or CH3、R3For H or CH3, and R4For
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
Specifically, formula described in wherein at least one (4) oligomer system is with such as formula (IIIc-M), formula (IIIc-A) or formula
(IIIc-VB) poly- (2,6 dimethyl phenylate) the oligomer expression of double bond phosphorus system containing unsaturated group,
Wherein m and n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
The implementation of above related invention, will be with the specific embodiment explanation in following embodiments.
The preparation method of poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system
In the present invention, synthesis phosphorus series bisphenols compound (I) first,
Wherein, R1、R2Or R3H or straight chain or branched-chain alkyl with 1 to 6 C atom are respectively indicated independently of one another,
Preferably H, methyl or ethyl；Then with bisphenol compound (I) and 2,6- xylenol in CuCl and aminated compounds (such as two
Butylamine (dibutylamine, DBA) or 4- dimethylaminopyridine (4-dimethylaminopyridine, DMAP)) catalysis under,
Synthesize poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system.
Specifically, the method for synthesizing poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system in formula (2) comprising making
Object (I) and 2,6- xylenol are closed, in CuCl and aminated compounds (such as dibutyl amine (dibutylamine) or 4- dimethylamino
Pyridine (4-dimethylaminopyridine)) catalysis under reacted, be made poly- (2, the 6 dimethyl phenylate) bis-phenol of phosphorus system
Oligomer, wherein R1And R2Each expression H or straight chain or branched-chain alkyl with 1 to 6 C atom independently of one another, preferably H,
Methyl or ethyl；
In the above method of the present invention, wherein obtained poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of phosphorus system includes extremely
A kind of oligomer of few formula (3).
Specifically, in the above method of the present invention, wherein obtained poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system
System includes the oligomer of at least one formula (IIa) or formula (IIc').
In the above method of the present invention, work as R2When for hydrogen, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer packet of obtained phosphorus system
Containing the structure as shown in following formula (IIa):
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
In the above method of the present invention, work as R2For CH3When, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer packet of obtained phosphorus system
Containing the structure as shown in following formula (IIc'):
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
Carrying out rearrangement reaction (redistribution) again with bis-phenol and high molecular weight type PPO is a manufacture bis-phenol functional group
PPO method.However, rearrangement reaction again, often leads to the double distribution molecular weight of height because of side reaction.And the production of high molecular weight
Object, then because dissolubility is bad, impregnation is bad and influences it in the application of copper clad laminate.Good to obtain dissolubility, impregnation is good
Product, escape Traditional Thinking of the present invention, using PPO oligomer (SA-90 of such as SABIC) be starting material, by phosphorus system diphenol
Rearrangement reaction again is carried out with SA-90, and it is good to obtain dissolubility, it is good to glass impregnation, and there is the phosphorus system of flame-retarding characteristic simultaneously
Poly- (2,6 dimethyl phenylate) bis-phenol oligomer.
In the above method of the present invention, including making formula (I) and formula (5) poly- (2,6 dimethyl phenylate) oligomer:
Rearrangement reaction again is carried out under catalyzed, it is few poly- (2, the 6 dimethyl phenylate) bis-phenol of phosphorus system is made
Polymers, wherein
Y is indicated
P, q respectively indicates 0 to 50 integer independently of one another.
In the above method of the present invention, wherein obtained poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of phosphorus system includes extremely
A kind of oligomer of few formula (3).
Specifically, in the above method of the present invention, wherein obtained poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system
System includes the oligomer of at least one formula (IIc).
In the above method of the present invention, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of obtained phosphorus system includes such as following formula
(IIc) structure shown in:
Wherein, R1For H, CH3Or C2H5、R2For H or CH3And R3 is H or CH3。
The method for preparing poly- (the 2,6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group
The method for preparing poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group comprising by aforementioned system
Poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system by terminal hydroxyl structure alkali catalyst catalysis under, with metering system
Acid anhydride (methacrylic anhydride), allyl bromide, bromoallylene (allyl bromine) or 4- 1-chloro-4-methyl-benzene (4-
Chloromethylstyrene it) reacts, and poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group is made.
In the above method of the present invention, wherein obtained poly- (2,6 dimethyl benzenes of double bond phosphorus system containing unsaturated group
Ether) oligomer of the oligomer system including at least one formula (4).
Specifically, the obtained double bond phosphorus system poly- (2,6 dimethyl phenylate) containing unsaturated group of the above method of the present invention is few
Polymers comprising one of at least such as the oligomer of formula (IIIa) and formula (IIIc):
Wherein, R1、R2Or R3H or straight chain or branched-chain alkyl with 1 to 6 C atom are respectively indicated independently of one another,
Preferably H, methyl or ethyl and R4Indicate H or alkenyl with 1 to 10 C atom, aryl or combinations thereof, wherein comprising 0 to
3 O atoms, preferably
Specifically, the obtained double bond phosphorus system poly- (2,6 dimethyl phenylate) containing unsaturated group of the above method of the present invention is few
Polymers comprising such as the oligomer of formula (IIIa):
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
Specifically, the obtained double bond phosphorus system poly- (2,6 dimethyl phenylate) containing unsaturated group of the above method of the present invention is few
Polymers comprising such as formula (IIIc) or the oligomer of (IIIc'):
Wherein, R1For H, CH3Or C2H5、R2For H or CH3、R3For H or CH3, and R4For
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
In the above method of the present invention, wherein the alkali catalyst system is selected from by potassium carbonate (K2CO3), sodium carbonate (Na2CO3)、
Potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium bicarbonate (NaHCO3), or combinations thereof composed by group.
In the above method of the present invention, wherein obtained poly- (2, the 6 dimethyl phenylate) oligomerization of double bond phosphorus system containing unsaturated group
Object system is indicated with the oligomer of formula (IIIc-M):
Wherein m or n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
In the above method of the present invention, wherein obtained poly- (2, the 6 dimethyl phenylate) oligomerization of double bond phosphorus system containing unsaturated group
Object system is indicated with the oligomer of formula (IIIc-A):
Wherein m or n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
In the above method of the present invention, wherein obtained poly- (2, the 6 dimethyl phenylate) oligomerization of double bond phosphorus system containing unsaturated group
Object system is indicated with the oligomer of formula (IIIc-VB):
Wherein m or n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
The thermosetting compound and preparation method of poly- (the 2,6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group
Poly- (the 2,6 dimethyl phenylate) oligomer of double bond phosphorus system by formula (4) containing unsaturated group is using peroxide as free radical
Under initiator, the reaction of unsaturated group is carried out, can obtain that there is fire-retardant, low-k, low dielectric absorption and the transfer of high glass
The thermosetting compound of temperature.
In the above-mentioned preparation heat cure object space method of the present invention comprising anti-solidify with free radical starting agent by formula (4)
It answers, can obtain that there is fire-retardant, low-k, the thermosetting compound of low dielectric absorption and high glass transition temperature.
The present invention is above-mentioned to be prepared in solidfied material heat cure object space method, wherein the free radical starting agent includes peroxidating
Object, preferably three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, (TBCP)).
In the above-mentioned preparation heat cure object space method of the present invention comprising by the double bond phosphorus containing unsaturated group of such as formula (IIIc-M)
It is poly- (2,6 dimethyl phenylate) oligomer, and free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl
Peroxide, (TBCP)), curing reaction is carried out, can obtain that there is fire-retardant, low-k, low dielectric absorption and high glass turn
Move the thermosetting compound of temperature.
In the above-mentioned preparation heat cure object space method of the present invention comprising by the double bond phosphorus containing unsaturated group of such as formula (IIIc-A)
It is poly- (2,6 dimethyl phenylate) oligomer, and free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl
Peroxide, (TBCP)), curing reaction is carried out, can obtain that there is fire-retardant, low-k, low dielectric absorption and high glass turn
Move the thermosetting compound of temperature.
In the above-mentioned preparation heat cure object space method of the present invention comprising by the double bond containing unsaturated group of such as formula (IIIc-VB)
Poly- (2, the 6 dimethyl phenylate) oligomer of phosphorus system, and free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl
Peroxide, (TBCP)), curing reaction is carried out, can obtain that there is fire-retardant, low-k, low dielectric absorption and high glass turn
Move the thermosetting compound of temperature.
Detailed description of the invention
Fig. 1 is the phosphorus system methylphenol of synthesis1H-NMR spectrum.
Fig. 2 is that the LC/MS of formula (IIa) oligomer schemes.
Fig. 3 is formula (IIc) oligomer and (IIIc-VB) oligomer1H-NMR spectrum is repeatedly schemed.
Fig. 4 is formula (IIIc-VB) oligomer with initiator (t-butyl cumyl peroxide (TBCP)) cured heat
The DMA of solidfied material schemes
Fig. 5 is formula (IIIc-VB) oligomer with initiator (t-butyl cumyl peroxide (TBCP)) cured heat
The TMA of solidfied material schemes
Fig. 6 is formula (IIIc-VB) oligomer with initiator (t-butyl cumyl peroxide (TBCP)) cured heat
The elliptical polarized light curve graph of solidfied material.
Specific embodiment
The present invention is further illustrated for following embodiment, only non-to limit the scope of the invention, any to be familiar with
Technical field person belongs to model of the invention without prejudice to the modification and transformation reached is able under spirit of the invention
It encloses.
The synthesis of 1 phosphorus system methylphenol of embodiment
Take the miscellaneous -10- phosphorus phenanthrene -10- oxide 15.9g of parahydroxyacet-ophenone 10.0g (73.4mmol), 9,10- dihydro-9-oxy
(73.4mmol), 2,6- xylenol 44.40g (73.4*5mmol), p-methyl benzenesulfonic acid 0.64g (9,10- dihydro-9-oxy is miscellaneous-
The 4wt% of 10- phosphorus phenanthrene -10- oxide), it reacts 24 hours for 130 DEG C in a nitrogen environment, pumping filtering while hot after reaction
Filter cake is taken, filter cake is cleaned with methanol obtains white powder for several times, and filter cake is placed in 80 DEG C of vacuum drying ovens dryings, yield after pumping filtering
About 85%.
Fig. 1 is monomer (1)1H NMR figure, it is possible to find CH3(a) in 1.6ppm, CH3(b) in 2.0ppm.The feature of Ar-OH
Peak 9.4ppm.In addition,3138.0ppm signal can be seen in P NMR, can confirm that structure is correct.
The synthesis (IIa) of 2 phosphorus system methyl polyoxy dimethylbenzene of embodiment
Take CuCl 0.079g (0.8mmole), DMAP 0.095g (0.78mmole) with N- crassitude (1-
Methyl-2-pyrrolidone, NMP) 25mL as solvent, be passed through at room temperature oxygen reaction after ten minutes be added monomer (1)
0.739g(1.62mmole)、2,6- xylenol0.979g (8.01mmole) reacts 4 hours for 40 DEG C under oxygen atmosphere,
Filtrate is filtered to take in pumping after reaction, and filtrate with methanol precipitation and is cleaned for several times, after pumping filtering, filter cake vacuum drying oven
Vacuum drying obtains khaki product IIa at 80 DEG C.The LC/MS that Fig. 2 is IIa schemes.It can be observed that 697.5m/z is n=1
Molecular weight.The molecular structure of n=2 to n=11 is also found in Fig. 2.
The synthesis of embodiment 3 formula (IIc) phosphorus system methyl polyoxy dimethylbenzene
Bis-phenol 4.0g (8.76mmol), the SABIC SA904g (8.76x 3.8mmol), benzoyl peroxide first of Example 1
Acyl (benzoyl peroxide) 0.404g (1/40mol of SA90), using NMP as solvent, 130 DEG C of reactions in a nitrogen environment
12 hours, reaction terminated to be precipitated and cleaned for several times with methanol/water, obtains coffee-like powder, filter cake is placed in 70 DEG C after pumping filtering
Vacuum drying oven is dry, yield about 90%.According to1H NMR figure, it is possible to find in 6-8.5ppm it can be seen that two stretch benzene phosphinate
The hydrogen signal of biphenyl in (biphenylene phosphinate) structure.GPC data analysis (is to purge with tetrahydrofuran (THF)
Liquid, using polystyrene as standard items), it is possible to find the number average molecular weight and weight average molecular weight of SA-90 is respectively 1508 Hes
3978 grams/mole, and the number average molecular weight of formula (IIIc) and weight average molecular weight are respectively 787 and 2625 grams/mole.
Again after rearrangement reaction, average molecular weight has the tendency that reduction, is conducive to dissolubility and impregnation for display.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis formula (IIIc-M) metering system (MMA) base of embodiment 4
Synthesized 1.0 grams of the formula (IIc) out of Example 3, DMAP 0.01g (2mol%of metering system acid anhydride) are with diformazan
Yl acetamide (DMAc) 15mL reacts at room temperature 1 hour under ar gas environment as solvent, is subsequently added into metering system acid anhydride 0.665g
It is warming up to 45 DEG C after reacting 3 hours at room temperature, reacts 24 hours, reaction terminates to be saturated NaHCO3(washing off acid) is precipitated in aqueous solution
And wash with water for several times, filter cake is placed in 50 DEG C of vacuum drying ovens dryings, yield about 85% after pumping filtering.It is red by Fourier transform
It can be seen that in-O-C=O- characteristic peak 1735cm in the analysis of external spectrum (FTIR) data-1With-C=C- characteristic peak in 1649cm-1。
Wherein m and n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Via formula (IIIc-M) oligomer1H NMR figure can find there is acrylic group in 2.0,5.9 and 6.3ppm
(acrylate) characteristic peak, display structure are correct.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis formula (IIIc-A) allylation of embodiment 5
Synthesized 1.0 grams of the formula (IIc) out of Example 3,0.23 gram of allyl bromide, bromoallylene, K2CO30.1 gram is worked as with DMAc 15mL
Make solvent, be warming up to 65 DEG C in a nitrogen environment, react 24 hours, be cooled to room temperature after reaction, filter salt, collects filter
Filtrate is poured into the full conjunction saline solution of ice, takes filter cake after pumping filtering by liquid, is put into 60 DEG C of vacuum drying ovens drying, it is micro- to obtain khaki
Cemented body, yield 70%.By can see in the analysis of FTIR data in 915cm-1Acrylic characteristic peak.
Wherein m and n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Via formula (IIIc-A) oligomer1H NMR figure can find there is allyl in 4.8,5.3 and 6.1ppm
(allylic) characteristic peak, display structure are correct.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis formula (IIIc-VB) vinyl phenyl of embodiment 6
Synthesized 1.0 grams of formula (IIc) oligomer out of Example 3,1.4 grams of 4- 1-chloro-4-methyl-benzene, K2CO30.1 gram with
DMAc 15mL is reacted 12 hours for 120 DEG C in a nitrogen environment as solvent, is precipitated and is cleaned for several times with ethyl alcohol after reaction
Khaki powder is obtained, filter cake is placed in 80 DEG C of vacuum drying ovens dryings, yield about 88% after pumping filtering.
Wherein m and n respectively indicates 0 to 30 integer, preferably 0 to 20 integer independently of one another.
Fig. 3 is formula (IIc) oligomer and formula (IIIc-VB) oligomer1H NMR figure.It can discoverable type (IIc) widow by Fig. 3
The disappearance of polymers OH functional group signal (4.3-4.6ppm), with formula (IIIc-VB) oligomer end 4- 1-chloro-4-methyl-benzene knot
Structure 5.2 (=CH, be denoted as 1), 5.8 (=CH1, be denoted as 1 ') and 4.8 (CH2, it is denoted as 3) number characteristic peak.
The preparation of the phosphorus system ethyl polyoxy dimethylbenzene thermosetting compound of 7 formula of embodiment (IIIc-M) metering system (MMA) base
With analysis
It is the molten of 30wt% that 1.0 grams of formula (IIIc-M) oligomer of Example 4, which prepare solid content as solvent with NMP,
Liquid after being completely dissolved, and is added three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (additive amount is
1wt%) progress radical reaction can be obtained film and be placed in circulation baking oven with the most of solvent of 110 DEG C of heating drying in 12 hours
Afterwards, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is two hours each.Glass substrate is finally dipped to phenol film in water to be detached from, and is surveyed
Its fixed related thermal properties.Using the glass transition temperature of thermosetting compound measured by Dynamic Mechanical Analyzer (DMA) in Fig. 4,
Glass transition temperature is 277 DEG C.The part dielectric constant (Dk) measures n when wavelength is 633nm by ellipsograph
(Refractive index) is 1.55, utilizes Dk=1.1n2Obtaining formula (IIIc-M) thermosetting compound is 2.64 (U), shows its tool
There is rather low dielectric property.
The preparation and analysis of the phosphorus system ethyl polyoxy dimethylbenzene thermosetting compound of 8 formula of embodiment (IIIc-A) allylation
It is the molten of 30wt% that 1.0 grams of formula (IIIc-A) oligomer of Example 6, which prepare solid content as solvent with NMP,
Liquid after being completely dissolved, and is added three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (additive amount is
1wt%) progress radical reaction can be obtained film and be placed in circulation baking oven with the most of solvent of 110 DEG C of heating drying in 12 hours
Afterwards, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is two hours each.Glass substrate is finally dipped to phenol film in water to be detached from, and is surveyed
Its fixed related thermal properties.Glass transition temperature using thermosetting compound measured by Dynamic Mechanical Analyzer (DMA) is 294 DEG C；It is situated between
The part electric constant (Dk), measuring n (Refractive index) when wavelength is 633nm by ellipsograph is 1.59, utilizes Dk
=1.1n2Obtaining formula (IIIc-A) thermosetting compound is 2.78 (U)
The preparation and analysis of the phosphorus system ethyl polyoxy dimethylbenzene thermosetting compound of 9 formula of embodiment (IIIc-VB) vinyl phenyl
It is the molten of 30wt% that 1.0 grams of formula (IIIc-VB) oligomer of Example 6, which prepare solid content as solvent with NMP,
Liquid after being completely dissolved, and is added three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (additive amount is
1wt%) progress radical reaction can be obtained film and be placed in circulation baking oven with the most of solvent of 110 DEG C of heating drying in 12 hours
Afterwards, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is two hours each.Glass substrate is finally dipped to phenol film in water to be detached from, and is surveyed
Its fixed related thermal properties.Using the glass transition temperature of thermosetting compound measured by Dynamic Mechanical Analyzer (DMA) in Fig. 4,
Glass transition temperature is 314 DEG C；In addition, the glass transition temperature of thermosetting compound is measured in Fig. 5 by thermal analyzer (TMA),
Glass transition temperature is 302 DEG C, shows that material possesses excellent thermal property.The part dielectric constant (Dk), exists by ellipsograph
Wavelength measures n (Refractive index) when being 633nm be 1.50, utilizes Dk=1.1n2Obtain formula (IIIc-VB) thermosetting compound
For 2.48 (U), it is shown with rather low dielectric property, referring to Fig. 6.
Claims (24)
1. a kind of poly- (2,6 dimethyl phenylate) oligomer of phosphorus system, it includes the structures of such as following formula (2):
Wherein group out of the ordinary has following meanings:
P1Expression be not present or
P2It indicates
R1、R2、R3H or straight chain or branched-chain alkyl with 1 to 6 C atom are respectively indicated independently of one another；
R4Indicate H or the alkenyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or combinations thereof；
M, n respectively indicates 0 to 30 integer independently of one another.
2. oligomer as claimed in claim 1, formula described in wherein at least one (2) oligomer system is with such as formula (3) phosphorus system poly- (2,6 two
Methyl phenylate) expression of bis-phenol oligomer,
Wherein P1、P2、R1、R2、R3, m and n system it is as defined in claim 1.
3. oligomer as claimed in claim 2, formula described in wherein at least one (3) oligomer system is with such as formula (IIa) or formula (IIc) phosphorus
It is that poly- (2,6 dimethyl phenylate) bis-phenol oligomer indicates,
Wherein R1、R2、R3, m and n system it is as defined in claim 1.
4. oligomer as claimed in claim 3, (IIc) the oligomer system of formula described in wherein at least one is poly- with such as formula (IIc') phosphorus system
The expression of (2,6 dimethyl phenylate) bis-phenol oligomer,
Wherein R1、R3, m and n system it is as defined in claim 1.
5. oligomer as claimed in claim 1, wherein formula (2) oligomer system described in described at least one contains insatiable hunger with such as formula (4)
It is indicated with the double bond phosphorus system of base poly- (2,6 dimethyl phenylate) oligomer,
Wherein P1、P2、R1、R2、R3, m and n system it is as defined in claim 1；And
R’4Indicate the alkenyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or combinations thereof.
6. oligomer as claimed in claim 5, wherein R '4For
7. oligomer as claimed in claim 5, formula described in wherein at least one (4) oligomer system is with such as formula (IIIa) or formula (IIIc)
Poly- (2,6 dimethyl phenylate) the oligomer expression of double bond phosphorus system containing unsaturated group,
Wherein R1、R2、R3, m and n system as defined in claim 1, and
R4It indicates
8. oligomer as claimed in claim 7, (IIIc) the oligomer system of formula described in wherein at least one contains insatiable hunger with such as formula (IIIc')
It is indicated with the double bond phosphorus system of base poly- (2,6 dimethyl phenylate) oligomer,
Wherein, R1、R3, m and n system as defined in claim 1, and
R4 is indicated
9. such as the oligomer of any one of claims 1 to 8, wherein the R1、R2Or R3H, CH are respectively indicated independently of one another3Or
C2H5, and m and n respectively indicate 0 to 20 integer independently of one another.
10. oligomer as claimed in claim 5, formula described in wherein at least one (4) oligomer system is with such as formula (IIIc-M), formula
(IIIc-A) or double bond phosphorus system poly- (2,6 dimethyl phenylate) oligomer of the formula (IIIc-VB) containing unsaturated group indicates,
Wherein m and n system is as defined in claim 1.
11. a kind of method for preparing formula as claimed in claim 2 (3) oligomer comprising make formula (I)
With 2,6 xylenols are reacted at CuCl and aminated compounds catalysis, poly- with formula (3) the phosphorus system for being made described
(2,6 dimethyl phenylate) bis-phenol oligomer, wherein R1, R2And R3System is as defined in claim 1.
12. such as the method for claim 11, wherein the aminated compounds system includes dibutyl amine or 4- dimethylaminopyridine.
13. such as the method for claim 11 or 12, wherein obtained described formula (3) phosphorus system poly- (2,6 dimethyl phenylate) is few
Polymers system includes at least one formula (IIa) as claimed in claim 3 or (IIc') oligomer as claimed in claim 4.
14. a kind of method for preparing formula as claimed in claim 2 (3) oligomer, including making formula (I):
Wherein, R1, R2And R3System is as defined in claim 1；
With poly- (the 2,6 dimethyl phenylate) oligomer of formula (5):
Wherein,
Y is indicated
With
P, q respectively indicates 0 to 50 integer independently of one another；
Rearrangement reaction again is carried out under catalyzed, it is poly- with formula as claimed in claim 2 (3) the phosphorus system for being made described
(2,6 dimethyl phenylate) bis-phenol oligomer.
15. such as the method for claim 14, wherein obtained described formula (3) bis-phenol phosphorus system poly- (2,6 dimethyl phenylate) is few
Polymers system includes at least one described formula (IIc) oligomer as claimed in claim 3.
16. a kind of method for preparing formula as claimed in claim 5 (4) comprising by described formula (3) the phosphorus system as claimed in claim 2
Poly- (2,6 dimethyl phenylate) bis-phenol oligomer, under the catalysis of alkali catalyst, with methacrylic anhydride, allyl bromide, bromoallylene or 4- chloromethyl
Styrene reaction, and double bond phosphorus system poly- (2, the 6 dimethyl phenylate) oligomer of the formula (4) containing unsaturated group is made.
17. such as the method for claim 16, wherein poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of formula (3) phosphorus system includes
Formula (IIc) as claimed in claim 3.
18. such as the method for claim 16 or 17, wherein the alkali catalyst system is selected from by potassium carbonate (K2CO3), sodium carbonate
(Na2CO3), potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium bicarbonate (NaHCO3) or combinations thereof composed by group.
19. such as the method for claim 16 or 17, wherein the obtained double bond phosphorus system of the formula (4) containing unsaturated group is poly-
(2,6 dimethyl phenylate) oligomer system includes at least one formula (IIIa) as claimed in claim 7 or the oligomer of (IIIc).
20. such as the method for claim 19, wherein obtained double bond phosphorus system poly- (2,6 two of the formula (4) containing unsaturated group
Methyl phenylate) oligomer include formula (IIIc-M) such as claim 10, formula (IIIc-A) or formula (IIIc-VB) oligomer.
21. a kind of thermosetting compound comprising carry out curing reaction with free radical starting agent by formula as claimed in claim 5 (4) and given birth to
At thermosetting compound.
22. such as the thermosetting compound of claim 21, wherein formula as claimed in claim 5 (4) includes the formula such as claim 10
(IIIc-M), formula (IIIc-A) or formula (IIIc-VB).
23. such as the thermosetting compound of claim 21 or 22, wherein the free radical starting agent includes peroxide.
24. such as the thermosetting compound of claim 21 or 22, wherein the free radical starting agent includes three-level butyl peroxy isopropylbenzene
(t-butyl cumyl peroxide,TBCP)。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0275545A1 (en) * | 1987-01-07 | 1988-07-27 | Bayer Ag | Oligomers and polymers with polyphenylene ether blocks which contain phosphorus and compositions thereof with other polymers |
| CN101747378A (en) * | 2008-12-02 | 2010-06-23 | 长春人造树脂厂股份有限公司 | Phosphorous compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275545A1 (en) * | 1987-01-07 | 1988-07-27 | Bayer Ag | Oligomers and polymers with polyphenylene ether blocks which contain phosphorus and compositions thereof with other polymers |
| CN101747378A (en) * | 2008-12-02 | 2010-06-23 | 长春人造树脂厂股份有限公司 | Phosphorous compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Catalyst-free synthesis of phosphinated poly(2,6-dimethyl-1,4- phenylene oxide) with high-Tg and low-dielectric characteristic;Ching Hsuan Lin, et al;《Polymer Degradation and Stability》;20131204;第99卷;第105-110页 * |
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