CN106565951A - Phosphorus series poly(2,6-dimethylphenyl ether) oligomer, and preparation method and thermocuring product thereof - Google Patents
Phosphorus series poly(2,6-dimethylphenyl ether) oligomer, and preparation method and thermocuring product thereof Download PDFInfo
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Abstract
The invention relates to a phosphorus series poly(2,6-dimethylphenyl ether) oligomer, and a preparation method and a thermocuring products thereof. The unsaturated group-containing double-bond phosphorus series poly(2,6-dimethylphenyl ether) oligomer can be further used for preparing the flame-retardant thermocuring product, and the thermocuring product has the advantages of good flame retardation property, low dielectric constant, low dielectric loss 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 its preparation method.Wherein, double bond phosphorus system poly- (2,6 dimethyl phenylate) oligomer of the present invention containing unsaturated group can be hardened further to prepare fire retardant thermosetting compound, and described thermosetting compound has anti-flammability, low-k, low dielectric absorption and high glass transition temperature.
Background technology
With the progress of semiconductor technology, the size of component also constantly reduces, and enters in micron field, then single layer conductor is not applied and used, it is necessary to develop towards three-dimensional space, thus it is online in necessary construction multiple layer metal, the demand of development could be met.In the inline mechanism journey of multiple layer metal, mainly there are two problems to affect its efficiency:First, caused by plain conductor and dielectric substance layer signal propagation delays (RC delay)；2nd, be between plain conductor signal interference (cross talk), in addition signal transmission speed and dielectric constant square be inversely proportional to it is proportional with dielectric absorption, therefore develop dielectric materials be problem important now.
Poly- (2,6 benzyl ethers) (poly (2,6-dimethyl-1,4-phenylene oxide) or abbreviation PPO) be a kind of engineering plastics, the thermal plastic high polymer [1] developed by the A.S.Hay of unusual (General Electric) company of the U.S. in 1956.PPO structures are firm, and cause makes it have high glass transition temperature (about 210 DEG C of Tg), high-tensile, rigidity, impact strength, creep resistance, and low-expansion coefficient (CTE：2.9×10-5In/ ℉, -20 ℉～150 ℉) etc. characteristic, except this, PPO has good resistance to solvent, acidproof, alkaline-resisting, and low water absorption.Macromolecule method shaping often to project, and PPO has low molding shrinkage.In terms of electrical characteristic, PPO has low-k.
To reach the requirement of high-performance and high dimensional stability, copper clad laminate resin needs to seek thermosetting.But for fear of PPO structural relations itself, so that self-crosslinking having any problem property of hardening, limit PPO to develop and application in substrate, scholar Ueda et al. [2] is with oxidative coupling by 2,6- xylenols (2,6-Dimethylphenol) with 2- pi-allyl -6- cresols (2-Allyl-6-methylphenol) copolymerization, obtain the PPO that side chain has pi-allyl, PPO after modification, but itself becomes thermosetting polymer, after modified PPO hardening, still with high Tg, and low dielectric constant.So, it is not good to the impregnation of glass fibre because PPO has HMW so as to which with a relatively high stickiness, and solubility is not good, and limit its application in copper clad laminate.
2006, Ishii et al. synthesizes distant chela PPE giant molecule monomers (the telechelic PPE macromonomers of low-molecular-weight, PPE-M), and reacted the phenol terminal groups and 4- 1-chloro-4-methyl-benzenes of described giant molecule monomer, and the PPO compounds of styrene end are arrived, shown in vinyl phenyl PPE giant molecule monomers (VB-PPE-M) of its structure such as formula (1) [3].PPE-M and epoxy resin and cyanate are carried out copolymerization by Peters in 2007 et al. so as to which the performance of thermosetting compound is substantially improved [4].2011, Peters et al. [5] by commodity PPE-M under SABIC house flags (or claimSA90 terminal phenolic group) is modified so as to which end has unsaturated double-bond structure, as shown in formula (1).When PPE-M is imported containing methacrylate (methacrylate) terminal groups, methylpropenyl PPE giant molecule monomers (M-PPO-M) of its structural formula such as formula (1), its trade name NORYLTMResin SA 9000。
Due to the development of printed circuit board (PCB) now, the requirement of the aspects such as electrical properties, thermal property and flame retardancy for high frequency substrate is very high, especially V-0 grades must be reached in the fire retardant tests of UL-94, therefore the space that material still makes progress in this regard, PPO could be caused to meet the demand of market today, increase its using value.However, PPO has flammability, it is impossible to reach the requirement of electronic grade product UL-94V-0.In recent years, organic phosphorus compound is studied goes out to have preferred resistance to combustion characteristic for high molecular polymer, and compared to halogen-containing flame retardant, organic phosphorus compound is that solid phase is fire-retardant, less likely produces smog and toxic gas.Known addition type flame retardant, in addition to it can reduce the engineering properties of material, as the migration of flame retardant molecule or volatilization and cause the decline of its resistance to fuel efficiency fruit.In early stage is studied, extra addition incombustible agent makes it possible to reach preferred fire retardant effect.For example scholar Leu et al. [6] is added into PPO using nitrogenous phosphorus flame retardant, because the nitrogen phosphorus of fire retardant takes advantage of altogether effect, is allowed to UL-94 and is reached V-0 grades.In addition in PPO and polystyrene (PS) blending system, though strengthen the impact strength of PPO, but it is situation about gliding at fire retardant aspect, incombustible agent need to again be added, to reach preferred fire retardant effect, therefore scholar Takeda et al. [7] inquires into the fire retardant effect to PPO/PS using different phosphorous aromatic series incombustible agents.It was found that the phosphorous incombustible agent of addition, can effectively reduce the self-extinguishing time of burning, its flame resistance is lifted.In addition, woods et al. disclosed a series of phosphorus systems derivative in 2014, it is with 9, miscellaneous -10- phosphorus phenanthrene -10- the oxides (9 of 10- dihydro-9-oxies, 10-dihydro-9-oxa-10-phosphaphenanthrene10-oxide, hereinafter referred to as DOPO), the phosphorus group for having fire-retardant is introduced directly in the structure of PPO, to replace extra addition incombustible agent [8].Its result reaches VTM-0 grades when phosphorus content is 1% in UL-94, and display can effectively lift its flame retardancy really by the importing of phosphorus-containing groups.
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
The content of the invention
The present disclosure generally relates to poly- (2, the 6 dimethyl phenylate) oligomer of phosphorus system, specifically, the present invention includes two kinds of aspects, first phosphorus group is imported in PPO, obtains the bis-phenol oligomer with phosphorus group, particularly poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system.Then poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of obtained phosphorus system modified again, is imported three kinds of unsaturated double-bonds, poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group is further obtained.For example by phosphorus system poly- (2,6 dimethyl phenylates) reaction of bis-phenol oligomer and 4- 1-chloro-4-methyl-benzenes obtains the phosphorus system PPO of styrol, because styrene group is low polarity and hydrophobic structure, will be with low-k and low dielectric absorption, to obtain the thermosetting compound with the low dielectric of flame retardancy.
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 is included such as the structure of following formula (2)：
Group wherein out of the ordinary has following meanings：
P1Expression do not exist or
P2Represent
R1、R2、R3It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
R4H or the thiazolinyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or its combination are represented, preferably
M, n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system
In poly- (2, the 6 dimethyl phenylate) oligomer of the above-mentioned phosphorus system of the present invention, wherein working as R4For H when, formula (2) is represented for poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system, and an at least formula (2) oligomer system with the oligomer of such as formula (3)：
Group wherein out of the ordinary has following meanings：
P1Expression do not exist or
P2Represent
R1、R2、R3It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
M, n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Specifically, an at least formula (3) oligomer system is represented with the oligomer of such as formula (IIa) or formula (IIc)：
Group wherein out of the ordinary has following meanings：
R1、R2、R3It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
M, n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Specifically, formula (IIa) is preferably：
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
Specifically, formula (IIc) is preferably：
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 being not H, formula (2) is poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group, and formula (2) the oligomer system of wherein at least one is represented with the oligomer of such as formula (4)：
Group wherein out of the ordinary has following meanings：
P1Expression do not exist or
P2Represent
R1、R2、R3It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
R’4When the thiazolinyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or its combination, preferably
M, n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Specifically, the formula of wherein at least one (4) oligomer system is represented with the oligomer of such as formula (IIIa) or formula (IIIc)：
Group wherein out of the ordinary has following meanings：
R1、R2、R3It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
R4H or the thiazolinyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or its combination are represented, preferably
M, n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Specifically, formula (IIIa) is preferably：
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
Specifically, formula (IIIc) is preferably：
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 (4) oligomer system described in wherein at least one is with the double bond phosphorus system poly- (2 of such as formula (IIIc-M), formula (IIIc-A) or formula (IIIc-VB) containing unsaturated group, 6 dimethyl phenylates) oligomer represents
Wherein m and n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
The enforcement of related invention above, by 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, phosphorus series bisphenols compound (I) is synthesized first,
Wherein, R1、R2Or R3H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl are each represented independently of one another；Then with bisphenol compound (I) and 2,6- xylenols are in CuCl and aminated compounds (such as dibutyl amine (dibutylamine,) or 4- dimethylaminopyridine (4-dimethylaminopyridine DBA, DMAP under)) being catalyzed, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of synthesis phosphorus system.
Specifically, phosphorus system poly- (2 in synthesis type (2), 6 dimethyl phenylates) bis-phenol oligomer method, it includes making compound (I) and 2,6- xylenols, are reacted, so that phosphorus system poly- (2 is obtained under CuCl with aminated compounds (such as dibutyl amine (dibutylamine) or DMAP (4-dimethylaminopyridine)) catalysis, 6 dimethyl phenylates) bis-phenol oligomer, wherein R1And R2It is each to represent H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl independently of one another；
In said method of the present invention, wherein poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of obtained phosphorus system includes the oligomer of at least one formula (3).
Specifically, in said method of the present invention, wherein poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of obtained phosphorus system includes the oligomer of at least one formula (IIa) or formula (IIc').
In said method of the present invention, work as R2For hydrogen when, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of obtained phosphorus system includes structure as shown in following formula (IIa)：
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
In said method of the present invention, work as R2For CH3When, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of obtained phosphorus system includes the structure as shown in following formula (IIc')：
Wherein, R1For H, CH3Or C2H5And R3For H or CH3。
Rearrangement reaction again (redistribution) is carried out as manufacture bis-phenol functional group's PPO methods with bis-phenol and HMW type PPO.However, rearrangement reaction again, often causes the double distribution molecular weight of height because of side reaction.And the product of HMW, then because dissolubility is not good, impregnation is not good and affects it in the application of copper clad laminate.It is good to obtain dissolubility, the good product of impregnation, escape Traditional Thinking of the present invention, the use of PPO oligomers (such as SA-90 of SABIC) is initiation material, phosphorus system diphenol and SA-90 are carried out into rearrangement reaction again, and it is good to obtain dissolubility, it is good to glass impregnation, and while poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system with flame-retarding characteristic.
In said method of the present invention, including making formula (I) and poly- (2, the 6 dimethyl phenylate) oligomer of formula (5)：
Rearrangement reaction again is carried out under catalyzed, so that poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system is obtained, wherein
Y is represented
P, q respectively represent independently of one another 0 to 50 integer.
In said method of the present invention, wherein poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of obtained phosphorus system includes the oligomer of at least one formula (3).
Specifically, in said method of the present invention, wherein poly- (2,6 dimethyl phenylate) bis-phenol oligomer system of obtained phosphorus system includes the oligomer of at least one formula (IIc).
In said method of the present invention, poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of obtained phosphorus system includes the structure as shown in following formula (IIc)：
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
Prepare the double bond phosphorus system poly- (2 containing unsaturated group, 6 dimethyl phenylates) oligomer method, it is included aforementioned obtained phosphorus system poly- (2,6 dimethyl phenylates) bis-phenol oligomer by terminal hydroxyl structure alkali catalyst catalysis under, with the reaction of metering system acid anhydride (methacrylic anhydride), allyl bromide, bromoallylene (allyl bromine) or 4- 1-chloro-4-methyl-benzenes (4-chloromethylstyrene), and poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group is obtained.
In said method of the present invention, wherein obtained described poly- (2,6 dimethyl phenylate) oligomer system of the double bond phosphorus system containing unsaturated group includes the oligomer of at least one formula (4).
Specifically, obtained poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group of said method of the present invention, it include as formula (IIIa) and formula (IIIc) oligomer one of at least：
Wherein, R1、R2Or R3H or straight chain or branched-chain alkyl with 1 to 6 C atom, preferably H, methyl or ethyl, and R are each represented independently of one another4H or the thiazolinyl with 1 to 10 C atom, aryl or its combination are represented, wherein comprising 0 to 3 O atom, preferably
Specifically, obtained poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group of said method of the present invention, it is included such as the oligomer of formula (IIIa)：
Wherein, R1For H, CH3Or C2H5、R3For H or CH3, and R4For
Specifically, obtained poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group of said method of the present invention, it includes the oligomer such as formula (IIIc) or (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 said method of the present invention, wherein described alkali catalyst system is selected from potassium carbonate (K2CO3), sodium carbonate (Na2CO3), potassium hydroxide (KOH), NaOH (NaOH), sodium acid carbonate (NaHCO3) or its constituted group of combination.
In said method of the present invention, wherein poly- (2,6 dimethyl phenylate) oligomer system of the obtained double bond phosphorus system containing unsaturated group is represented with the oligomer of formula (IIIc-M)：
Wherein m or n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
In said method of the present invention, wherein poly- (2,6 dimethyl phenylate) oligomer system of the obtained double bond phosphorus system containing unsaturated group is represented with the oligomer of formula (IIIc-A)：
Wherein m or n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
In said method of the present invention, wherein poly- (2,6 dimethyl phenylate) oligomer system of the obtained double bond phosphorus system containing unsaturated group is represented with the oligomer of formula (IIIc-VB)：
Wherein m or n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
The thermosetting compound and its preparation method of poly- (the 2,6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group
The double bond phosphorus system poly- (2 containing unsaturated group by formula (4), 6 dimethyl phenylates) oligomer with peroxide as free radical starting agent under, carry out the reaction of unsaturated group, can obtain with fire-retardant, the thermosetting compound of low-k, low dielectric absorption and high glass transition temperature.
In the above-mentioned preparation heat cure object space method of the present invention, it is included by formula (4), to carry out curing reaction with free radical starting agent, can obtain the thermosetting compound with fire-retardant, low-k, 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 described free radical starting agent includes peroxide, 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, it is included by the double bond phosphorus system poly- (2 containing unsaturated group of such as formula (IIIc-M), 6 dimethyl phenylates) oligomer, with free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, (TBCP)), carry out curing reaction, the thermosetting compound with fire-retardant, low-k, low dielectric absorption and high glass transition temperature can be obtained.
In the above-mentioned preparation heat cure object space method of the present invention, it is included by the double bond phosphorus system poly- (2 containing unsaturated group of such as formula (IIIc-A), 6 dimethyl phenylates) oligomer, with free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, (TBCP)), carry out curing reaction, the thermosetting compound with fire-retardant, low-k, low dielectric absorption and high glass transition temperature can be obtained.
In the above-mentioned preparation heat cure object space method of the present invention, it is included by the double bond phosphorus system poly- (2 containing unsaturated group of such as formula (IIIc-VB), 6 dimethyl phenylates) oligomer, with free radical starting agent, such as three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, (TBCP)), carry out curing reaction, the thermosetting compound with fire-retardant, low-k, low dielectric absorption and high glass transition temperature can be obtained.
Description of the drawings
Fig. 1 is the phosphorus system methylphenol of synthesis1H-NMR spectrum.
Fig. 2 schemes for the LC/MS of formula (IIa) oligomer.
Fig. 3 is formula (IIc) oligomer and (IIIc-VB) oligomer1H-NMR spectrum are repeatedly schemed.
Fig. 4 is the DMA figures of the thermosetting compound that formula (IIIc-VB) oligomer is solidified with initiator (t-butyl cumyl peroxide (TBCP))
Fig. 5 is the TMA figures of the thermosetting compound that formula (IIIc-VB) oligomer is solidified with initiator (t-butyl cumyl peroxide (TBCP))
Fig. 6 is the elliptical polarized light curve map of the thermosetting compound that formula (IIIc-VB) oligomer is solidified with initiator (t-butyl cumyl peroxide (TBCP)).
Specific embodiment
The present invention is further illustrated for following examples, is only not used to limit the scope of the present invention, and any person that is familiar with technical field is able to the modification and transformation reached under the spirit without prejudice to the present invention, belongs to the scope of the present invention.
The synthesis of the phosphorus system methylphenol of embodiment 1
Take parahydroxyacet-ophenone 10.0g (73.4mmol), 9, miscellaneous -10- phosphorus phenanthrene -10- oxide the 15.9g (73.4mmol) of 10- dihydro-9-oxies, 2,6- xylenol 44.40g (73.4*5mmol), p-methyl benzenesulfonic acid 0.64g (9, the 4wt% of the miscellaneous -10- phosphorus phenanthrene -10- oxides of 10- dihydro-9-oxies), in a nitrogen environment 130 DEG C are reacted 24 hours, filter cake is filtered to take in pumping while hot after reaction terminates, filter cake is cleaned with methyl alcohol and obtain for several times white powder, filter cake is placed in 80 DEG C of vacuum drying ovens and is dried by pumping after filtering, yield about 85%.
Fig. 1 is monomer (1)1H NMR scheme, it is possible to find CH3A () is in 1.6ppm, CH3B () is in 2.0ppm.The characteristic peak 9.4ppm of Ar-OH.In addition,31P NMR can be seen 38.0ppm signals, can confirm that structure is correct.
The synthesis (IIa) of the phosphorus system methyl polyoxy dimethylbenzene of embodiment 2
CuCl 0.079g (0.8mmole), DMAP 0.095g (0.78mmole) are taken with N- crassitude (1-Methyl-2-pyrrolidone, NMP) 25mL is as solvent, be passed through at room temperature oxygen reaction add after 10 minutes monomer (1) 0.739g (1.62mmole),2,6- Xylenol0.979g (8.01mmole), 40 DEG C are reacted 4 hours under oxygen atmosphere, and filtrate is filtered to take in pumping after reaction terminates, by filtrate is with methyl alcohol precipitation and cleans for several times, after pumping is filtered, filter cake vacuum drying oven vacuum drying at 80 DEG C obtains khaki product IIa.Fig. 2 schemes for the LC/MS of IIa.It is observed that 697.5m/z is the molecular weight of n=1.The molecular structure of n=2 to n=11 is also found in Fig. 2.
The synthesis of formula (IIc) phosphorus of embodiment 3 system methyl polyoxy dimethylbenzene
The bis-phenol 4.0g (8.76mmol) of Example 1, SABIC SA904g (8.76x 3.8mmol), benzoyl peroxide (benzoyl peroxide) 0.404g (1/40mol of SA90), with NMP as solvent, in a nitrogen environment 130 DEG C are reacted 12 hours, reaction terminates to separate out with methanol/water and clean for several times, obtain coffee-like powder, filter cake is placed in 70 DEG C of vacuum drying ovens and is dried by pumping after filtering, yield about 90%.According to1H NMR scheme, it is possible to find can see the two hydrogen signals for stretching biphenyl in benzene phosphinate (biphenylene phosphinate) structure in 6-8.5ppm.GPC data analysis is (with tetrahydrofuran (THF) to purge with liquid, with polystyrene as standard items), the number average molecular weight and weight average molecular weight that SA-90 can be found is respectively 1508 and 3978 grams/mole, and the number mean molecule quantity and weight average molecular weight of formula (IIIc) are respectively 787 and 2625 grams/mole.After showing rearrangement reaction again, mean molecule quantity has the trend of reduction, is conducive to dissolubility and impregnation.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis type (IIIc-M) metering system (MMA) base of embodiment 4
1.0 grams of formula (IIc), the DMAP 0.01g (2mol%of metering system acid anhydrides) gone out synthesized by Example 3 is with dimethyl acetamide (DMAc) 15mL as solvent, room temperature reaction 1 hour under ar gas environment, it is subsequently added into after reacting 3 hours under metering system acid anhydride 0.665g room temperatures and is warming up to 45 DEG C, reaction 24 hours, reaction terminates with saturation NaHCO3The aqueous solution is separated out (washing acid off) and is cleaned for several times with water, and filter cake is placed in 50 DEG C of vacuum drying ovens and is dried by pumping after filtering, yield about 85%.By can see in-O-C=O- characteristic peak 1735cm in fourier transform infrared spectroscopy (FTIR) data analysis-1With-C=C- characteristic peaks in 1649cm-1。
Wherein m and n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Via formula (IIIc-M) oligomer1H NMR figures can be found 2.0,5.9, and 6.3ppm has the characteristic peak of acrylic group (acrylate), shows that structure is correct.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis type (IIIc-A) allylation of embodiment 5
1.0 grams of formula (IIc), 0.23 gram of allyl bromide, bromoallylene, the K gone out synthesized by Example 32CO30.1 gram with DMAc 15mL as solvent, 65 DEG C are warming up in a nitrogen environment, reaction 24 hours, reaction is cooled to room temperature after terminating, filter salt, collect filtrate, filtrate is poured in the full conjunction saline solution of ice, pumping takes filter cake after filtering, be put into 60 DEG C of vacuum drying ovens drying, obtain the micro- cemented body of khaki, yield 70%.By can see in 915cm in FTIR data analyses-1Acrylic characteristic peak.
Wherein m and n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Via formula (IIIc-A) oligomer1H NMR figures can be found 4.8,5.3, and 6.1ppm has the characteristic peak of pi-allyl (allylic), shows that structure is correct.
The phosphorus system ethyl polyoxy dimethylbenzene of synthesis type (IIIc-VB) vinyl phenyl of embodiment 6
1.0 grams of formula (IIc) oligomer, 1.4 grams of 4- 1-chloro-4-methyl-benzenes, the K gone out synthesized by Example 32CO30.1 gram with DMAc 15mL as solvent, in a nitrogen environment 120 DEG C are reacted 12 hours, reaction separated out with ethanol after terminating and cleans for several times khaki powder, filter cake is placed in 80 DEG C of vacuum drying ovens and is dried by pumping after filtering, yield about 88%.
Wherein m and n respectively represent independently of one another 0 to 30 integer, preferably 0 to 20 integer.
Fig. 3 is formula (IIc) oligomer and formula (IIIc-VB) oligomer1H NMR scheme.By Fig. 3 can discoverable type (IIc) oligomer OH functional group's signals (4.3-4.6ppm) disappearance, with with formula (IIIc-VB) oligomer end 4- 1-chloro-4-methyl-benzene structures in 5.2 (=CH, be denoted as 1), 5.8 (=CH1 is 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 formula (IIIc-M) metering system (MMA) base of embodiment 7 and analysis
1.0 grams of formula (IIIc-M) oligomer of Example 4 prepares solution of the solid content as 30wt% with NMP as solvent, after being completely dissolved, and add three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (addition is 1wt%) carries out radical reaction film is obtained being placed in circulation baking oven with after the most of solvent of 110 DEG C of heating drying in 12 hours, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is each two hours.Finally glass substrate is dipped to into phenol film in water to depart from, and determines its related thermal properties.Using the glass transition temperature of thermosetting compound measured by Dynamic Mechanical Analyzer (DMA) in Fig. 4, its glass transition temperature is 277 DEG C.Dielectric constant (Dk) part, it is 1.55 that n (Refractive index) is measured when wavelength is 633nm by ellipsograph, using Dk=1.1n2It is 2.64 (U) to obtain formula (IIIc-M) thermosetting compound, shows that it has at a fairly low dielectric property.
The preparation of the phosphorus system ethyl polyoxy dimethylbenzene thermosetting compound of formula (IIIc-A) allylation of embodiment 8 and analysis
1.0 grams of formula (IIIc-A) oligomer of Example 6 prepares solution of the solid content as 30wt% with NMP as solvent, after being completely dissolved, and add three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (addition is 1wt%) carries out radical reaction film is obtained being placed in circulation baking oven with after the most of solvent of 110 DEG C of heating drying in 12 hours, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is each two hours.Finally glass substrate is dipped to into phenol film in water to depart from, and determines its related thermal properties.It it is 294 DEG C using the glass transition temperature of thermosetting compound measured by Dynamic Mechanical Analyzer (DMA)；Dielectric constant (Dk) part, it is 1.59 that n (Refractive index) is measured when wavelength is 633nm by ellipsograph, using Dk=1.1n2It is 2.78 (U) to obtain formula (IIIc-A) thermosetting compound
The preparation of the phosphorus system ethyl polyoxy dimethylbenzene thermosetting compound of formula (IIIc-VB) vinyl phenyl of embodiment 9 and analysis
1.0 grams of formula (IIIc-VB) oligomer of Example 6 prepares solution of the solid content as 30wt% with NMP as solvent, after being completely dissolved, and add three-level butyl peroxy isopropylbenzene (t-butyl cumyl peroxide, TBCP) (addition is 1wt%) carries out radical reaction film is obtained being placed in circulation baking oven with after the most of solvent of 110 DEG C of heating drying in 12 hours, regeneration temperature to 180 DEG C, 200 DEG C, 220 DEG C it is each two hours.Finally glass substrate is dipped to into phenol film in water to depart from, and determines its related thermal properties.Using the glass transition temperature of thermosetting compound measured by Dynamic Mechanical Analyzer (DMA) in Fig. 4, its glass transition temperature is 314 DEG C；In addition, measuring the glass transition temperature of thermosetting compound in Fig. 5 by thermal analyzer (TMA), its glass transition temperature is 302 DEG C, shows that material possesses excellent thermal property.Dielectric constant (Dk) part, it is 1.50 that n (Refractive index) is measured when wavelength is 633nm by ellipsograph, using Dk=1.1n2It is 2.48 (U) to obtain formula (IIIc-VB) thermosetting compound, shows that it has at a fairly low dielectric property, referring to Fig. 6.
Claims (24)
1. poly- (2, the 6 dimethyl phenylate) oligomer of a kind of phosphorus system, it is included such as the structure of following formula (2)：
Group wherein out of the ordinary has following meanings：
P1Expression do not exist or
P2Represent
R1、R2、R3H or straight chain or branched-chain alkyl with 1 to 6 C atom are each represented independently of one another；
R4Represent H or the thiazolinyl with 1 to 10 C atom and comprising 0 to 3 oxygen atom, aryl or its group
Close；
M, n respectively represent independently of one another 0 to 30 integer.
2. oligomer as claimed in claim 1, formula (2) the oligomer system described in wherein at least one is with such as formula (3) phosphorus system poly- (2,6
Dimethyl phenylate) bis-phenol oligomer represents,
Wherein P1、P2、R1、R2、R3, m and n systems as defined in claim 1.
3. oligomer as claimed in claim 2, formula (3) the oligomer system described in wherein at least one is with such as formula (IIa) or formula (IIc)
Poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system represents,
Wherein R1、R2、R3, m and n systems as defined in claim 1.
4. oligomer as claimed in claim 3, formula (IIc) the oligomer system described in wherein at least one is with such as formula (IIc') phosphorus system
Poly- (2,6 dimethyl phenylate) bis-phenol oligomer represents,
Wherein R1、R3, m and n systems as defined in claim 1.
5. oligomer as claimed in claim 1, wherein described formula (2) the oligomer system at least described in is contained with such as formula (4)
Poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system of unsaturated group represents,
Wherein P1、P2、R1、R2、R3, m and n systems as defined in claim 1；And
R’4Represent that there is 1 to 10 C atom and the thiazolinyl comprising 0 to 3 oxygen atom, aryl or its combination.
6. oligomer as claimed in claim 5, wherein R '4For
7. oligomer as claimed in claim 5, formula (4) the oligomer system described in wherein at least one is with such as formula (IIIa) or formula (IIIc)
Poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system containing unsaturated group represents,
Wherein R1、R2、R3, m and n systems as defined in claim 1, and
R4Represent
8. oligomer as claimed in claim 7, formula (IIIc) the oligomer system described in wherein at least one is with such as formula (IIIc') containing not
Poly- (2, the 6 dimethyl phenylate) oligomer of double bond phosphorus system of saturation base represents,
Wherein, R1、R3, m and n systems as defined in claim 1, and
R4 is represented
9. such as the oligomer of any one of claim 1 to 8, wherein described R1、R2Or R3Each H of expression independently of one another,
CH3Or C2H5, and m and n respectively represent independently of one another 0 to 20 integer.
10. oligomer as claimed in claim 5, formula (4) the oligomer system described in wherein at least one is with such as formula (IIIc-M), formula
(IIIc-A) or formula (IIIc-VB) containing unsaturated group poly- (2,6 dimethyl phenylate) the oligomer table of double bond phosphorus system
Show,
Wherein m and n systems are as defined in claim 1.
The method that 11. one kind prepare formula as claimed in claim 2 (3) oligomer, it includes making formula (I)
With 2,6 xylenols are reacted, so that described formula (3) is obtained under CuCl with aminated compounds catalysis
Phosphorus system poly- (2,6 dimethyl phenylate) bis-phenol oligomer, wherein R1,R2And R3System is as defined in claim 1.
The method of 12. such as claims 11, wherein described aminated compounds system includes dibutyl amine or 4- dimethylaminopyridines.
13. as claim 11 or 12 method, wherein obtained described formula (3) phosphorus system poly- (2,6 dimethyl phenylate)
Oligomer system includes at least one formula (IIa) as claimed in claim 3 or (IIc') oligomer as claimed in claim 4.
The method that 14. one kind prepare 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 represented With
P, q respectively represent independently of one another 0 to 50 integer；
Rearrangement reaction again is carried out under catalyzed, so that described formula as claimed in claim 2 (3) phosphorus is obtained
It is poly- (2,6 dimethyl phenylate) bis-phenol oligomer.
15. as claim 14 method, wherein obtained described formula (3) bis-phenol phosphorus system poly- (2,6 dimethyl phenylate)
Oligomer system includes at least one described formula (IIc) oligomer as claimed in claim 3.
The method that 16. one kind prepare formula as claimed in claim 5 (4), it is included described formula (3) as claimed in claim 2
Poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of phosphorus system, under the catalysis of alkali catalyst, with metering system acid anhydride, pi-allyl
Bromine or 4- 1-chloro-4-methyl-benzenes react, and described double bond phosphorus system poly- (2,6 of the formula (4) containing unsaturated group is obtained
Dimethyl phenylate) oligomer.
17. as claim 16 method, wherein poly- (2,6 dimethyl phenylate) the bis-phenol oligomer of described formula (3) phosphorus system
Including formula as claimed in claim 3 (IIc).
18. as claim 16 or 17 method, wherein described alkali catalyst system be selected from potassium carbonate (K2CO3), sodium carbonate
(Na2CO3) potassium hydroxide (KOH), NaOH (NaOH), sodium acid carbonate (NaHCO3) or its group
Close constituted group.
The method of 19. such as claims 16 or 17, wherein obtained double bond phosphorus system of the described formula (4) containing unsaturated group gathers
(2,6 dimethyl phenylate) oligomer system includes at least one as claimed in claim 7 formula (IIIa) or (IIIc's)
Oligomer.
20. as claim 19 method, wherein obtained double bond phosphorus system poly- (2,6 of the described formula (4) containing unsaturated group
Dimethyl phenylate) oligomer includes formula (IIIc-M) such as claim 10, formula (IIIc-A) or formula (IIIc-VB)
Oligomer.
A kind of 21. thermosetting compounds, it includes carrying out curing reaction institute by formula as claimed in claim 5 (4) and free radical starting agent
The thermosetting compound of generation.
22. as claim 21 thermosetting compound, 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. as claim 21 or 22 thermosetting compound, wherein described free radical starting agent include peroxide.
24. as claim 21 or 22 thermosetting compound, wherein described free radical starting agent include three-level butyl peroxy isopropylbenzene
(t-butyl cumyl peroxide,TBCP)。
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| TWI650344B (en) * | 2017-09-27 | 2019-02-11 | 國立中興大學 | Phosphoric phenyl ether oligo polymer having crosslinkable group, preparation method thereof, curing composition and cured product |
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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 |
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