CN105778096A - Manufacturing method and application of benzocyclobutenyl containing silicon resin - Google Patents
Manufacturing method and application of benzocyclobutenyl containing silicon resin Download PDFInfo
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- CN105778096A CN105778096A CN201410822000.XA CN201410822000A CN105778096A CN 105778096 A CN105778096 A CN 105778096A CN 201410822000 A CN201410822000 A CN 201410822000A CN 105778096 A CN105778096 A CN 105778096A
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Abstract
The invention provides a manufacturing method and application of benzocyclobutenyl containing silicon resin. Specifically, a benzocyclobutenyl containing silane monomer and a variety of silane monomers are subjected to hydrolytic copolymerization reaction to obtain organic silicon resin, then the organic silicon resin is heated for curing molding, and the obtained curing product is a novel high-temperature curing organic silicon resin with good temperature resistance and excellent electrical properties, and can be applied as a high performance resin matrix or packaging material in the electric industry, aerospace and other fields.
Description
Technical field
The invention provides a kind of organic siliconresin, be specifically related to a kind of can the manufacture method of silicone resin material of hot setting and application thereof containing benzocyclobutene group.
Background technology
Organic siliconresin is the veriety earlier that comes out in organosilicon material, there are many excellent properties of organosilicon material, optical property etc. such as excellent thermostability, weatherability, cold-hot impact, easy processing and excellence, the dielectric properties of silicones are excellent, remain stable in bigger temperature, humidity, frequency range.Organic siliconresin can be used for insullac, coating, moulding compound, laminated material, releasing agent, moistureproof and waterproof agent etc., is widely used in Aero-Space, electronic apparatus, building, machinery etc..
Benzocyclobutene (Benzocyclobutene, BCB) resin is also a class multifunctional macromolecule material, its molecule is heated and can form build high polymer by curing reaction, cured product has good temperature tolerance, chemical stability, excellent electric property, low hydroscopicity and good mechanical property etc., based on this, it is expected as combined with organosilicon material by benzocyclobutene to obtain new type functional material, many relevant reports utilize this feature just, have developed the multiple organosilicon material containing benzocyclobutene.
Gros etc. (U.S. patent Nos US4759847,1988) have synthesized the silane coupler of benzocyclobutene modification and can be used as binding agent.
The disiloxane monomer (CYCLOTENE3000 series) containing benzocyclobutene of the Dow Chemical Company's exploitation has good dielectric properties, shown in formula specific as follows:
Yang Shiyong et al. reports the silane small molecule monomer (J.Polym.Sci.Polym.Chem.2009,47,6246) introducing benzocyclobutene in phenyl siloxane, formula specific as follows:
Poplar military school etc. reports the modified silicon oil (Chinese invention patent application 201110367893.X) being introduced benzocyclobutene by side chain:
It is introduced in the performance improving silane to a certain extent by benzocyclobutene, widen its application, but these materials mostly are small-molecular-weight monomer, and ubiquity has synthesis condition harshness, initiation material to be difficult to obtain or relatively costly, material melting point is low, film property is poor, needs the problems such as pre-polymerization during use so that it is application is limited significantly.
In sum, this area has synthesis condition gentleness in the urgent need to developing one, and preparation cost is low, the silicone resin material containing benzocyclobutene unit of good processability.
Summary of the invention
It is an object of the invention to provide one and there is good temperature tolerance, close-burning organic siliconresin encapsulating material.
A first aspect of the present invention, it is provided that a kind of organic siliconresin containing benzocyclobutane thiazolinyl, described organic siliconresin is to prepare with the copolymerization that is hydrolyzed of the such as monomer shown in following formula A and the optional monomer as shown in following formula B:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, benzocyclobutane thiazolinyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
It is preferred that in described formula A, have at least a R (being preferably 1,2 or 3) not for benzocyclobutane thiazolinyl；And in described formula B, each R is not all benzocyclobutane thiazolinyl；
More preferably, described formula A monomer is chosen from the monomer of lower group (a):
(a) benzocyclobutane thiazolinyl trimethoxy silane, benzocyclobutene ethyl triethoxy silicane alkane, benzocyclobutane thiazolinyl trichlorosilane, phenyl (benzocyclobutane thiazolinyl) dimethoxysilane, phenyl (benzocyclobutane thiazolinyl) diethoxy silane, phenyl (benzocyclobutane thiazolinyl) dichlorosilane, dibenzo cyclobutane base dimethoxysilane, dimethyl (benzocyclobutane thiazolinyl) Ethoxysilane, methyl (benzocyclobutane thiazolinyl) dimethoxysilane, methyl (benzocyclobutane thiazolinyl) diethoxy silane, methyl (benzocyclobutane thiazolinyl) dichlorosilane, vinyl (benzocyclobutane thiazolinyl) dimethoxysilane, vinyl (benzocyclobutane thiazolinyl) diethoxy silane, vinyl (benzocyclobutane thiazolinyl) dichlorosilane, dimethylbiphenyl cyclobutane methoxylsilane, or its combination；
And described formula B monomer is chosen from the monomer of lower group (b):
(b) phenyl triethoxysilane, phenyltrimethoxysila,e, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, trimethylethoxysilane, methyl vinyl diethoxysilane, methyl trifluoro propyl diethoxy silane, dodecyltrimethoxysilane, tetraethyl orthosilicate, or its combination.
In another preference, in described formula A, having at least (being preferably a 1-3) R is C1～C4 alkoxyl.
In another preference, in described formula B, having at least (being preferably a 1-4) R is C1～C4 alkoxyl.
In another preference, in described formula A, each R is each independently selected from lower group: C1～C4 alkyl, C2～C4 thiazolinyl, C1～C4 alkoxyl.
In another preference, in described formula B, each R is each independently selected from lower group: C1～C4 alkyl, C1～C4 alkoxyl, phenyl.
In another preference, in the monomer that described hydrolysis copolymerization uses:
The molfraction a of formula A1 monomer is 0≤a≤0.8, and wherein, described formula A1 monomer has the structure shown in formula A, and in described formula A, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction b of formula A2 monomer is 0≤b≤0.6, and wherein, described formula A2 monomer has the structure shown in formula A, and in described formula A, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction c of formula A3 monomer is 0≤c≤0.3, and wherein, described formula A3 monomer has the structure shown in formula A, and in described formula A, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction d of formula B1 monomer is 0≤d≤0.3, and wherein, described formula B1 monomer has the structure shown in formula B, and in described formula B, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction e of formula B2 monomer is 0≤e≤0.5, and wherein, described formula B2 monomer has the structure shown in formula B, and in described formula B, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction f of formula B3 monomer is 0≤f≤0.4, and wherein, described formula B3 monomer has the structure shown in formula B, and in described formula B, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction g of formula B4 monomer is 0 < g≤0.3, and wherein, described formula B4 monomer has the structure shown in formula B, and in described formula B, has the group that 4 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
And be 0 during a, b, c difference.
In another preference, described organic siliconresin has average composition formula shown in formula I:
Wherein, a+b+c+d+e+f+g=1, and R1、R2、R3、R4、R5、R6、R7、R8Or R9It is independently selected from lower group: hydrogen, C1～C4 alkyl, C2～C4 thiazolinyl, aromatic radical, C8～C15 alkyl；It is preferred that R1、R2、R3、R4、R5、R6、R7、R8Or R9It is independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, dodecyl；
And the span of a, b, c, d, e, f, g is as follows: 0≤a≤0.8,0≤b≤0.6,0≤c≤0.3,0≤d≤0.3,0≤e≤0.5,0≤f≤0.4,0 < g≤0.3.
And be 0 during a, b, c difference.
In another preference, described organic siliconresin molecular weight is 1000-20000.
A second aspect of the present invention, it is provided that the preparation method of a kind of organic siliconresin as described in the first aspect of the invention, described method includes step:
In atent solvent, it is hydrolyzed polymerization with the such as monomer shown in following formula A and the optional monomer as shown in following formula B, obtains described organic siliconresin:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, benzocyclobutane thiazolinyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
It is preferred that in described formula A, have at least a R (being preferably 1,2 or 3) not for benzocyclobutane thiazolinyl；And in described formula B, each R is not all benzocyclobutane thiazolinyl.
Preferably, described method includes step:
In atent solvent, with the silane monomer containing benzocyclobutane thiazolinyl selected from lower group (a) be hydrolyzed polymerization selected from the silane monomer of lower group (b), obtain organic siliconresin shown in formula I:
(a) benzocyclobutane thiazolinyl trimethoxy silane, benzocyclobutene ethyl triethoxy silicane alkane, benzocyclobutane thiazolinyl trichlorosilane, phenyl (benzocyclobutane thiazolinyl) dimethoxysilane, phenyl (benzocyclobutane thiazolinyl) diethoxy silane, phenyl (benzocyclobutane thiazolinyl) dichlorosilane, dibenzo cyclobutane base dimethoxysilane, dimethyl (benzocyclobutane thiazolinyl) Ethoxysilane, methyl (benzocyclobutane thiazolinyl) dimethoxysilane, methyl (benzocyclobutane thiazolinyl) diethoxy silane, methyl (benzocyclobutane thiazolinyl) dichlorosilane, vinyl (benzocyclobutane thiazolinyl) dimethoxysilane, vinyl (benzocyclobutane thiazolinyl) diethoxy silane, vinyl (benzocyclobutane thiazolinyl) dichlorosilane, dimethylbiphenyl cyclobutane methoxylsilane, or its combination；
(b) phenyl triethoxysilane, phenyltrimethoxysila,e, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, methyl vinyl diethoxysilane, methyl trifluoro propyl diethoxy silane, trimethylethoxysilane, dodecyltrimethoxysilane, tetraethyl orthosilicate, or its combination.
In another preference, described hydrolytic-polymeric reaction carries out under acidic catalyst and/or water exist.
In another preference, described acidic catalyst is selected from lower group: hydrochloric acid, sulphuric acid, acetic acid, formic acid, or its combination.
In another preference, the mol ratio of described monomer, acid catalyst and water is preferably 1:0.2～20:0～10.
In another preference, described atent solvent is selected from lower group: benzene,toluene,xylene, trimethylbenzene, or its combination.
In another preference, described reaction temperature is 0～130 DEG C.
In another preference, the described response time is 3～35 hours.
In another preference, described method includes: at 0～30 DEG C, drips the mixed solution of formula A monomer and formula B monomer in the solvent be dissolved with acidic catalyst；
To, at the solution warms after described dropwising to 70～130 DEG C, continuing reaction.
In another preference, described method also includes: after dropwising, and after reacting a period of time, rises to and continues reaction at 70～130 DEG C at 0～30 DEG C.
In another preference, described method includes: at 0～30 DEG C, drips the mixed solution of formula A monomer and formula B monomer in the atent solvent be dissolved with acidic catalyst and water, then rises to and continues reaction at 70～130 DEG C.
In another preference, described method also includes: described organic siliconresin is heated up, thus sloughing micromolecular compound.
In another preference, described intensification is that decompression heats up.
In another preference, described decompression heats up as being decompressed to 9-11mba and/or being warming up to 140-160 DEG C
A third aspect of the present invention, it is provided that a kind of cured product, described cured product be with organic siliconresin as described in the first aspect of the invention individually or blended with the performed polymer of other curable molding after carry out curing molding and prepare.
In another preference, the performed polymer of other described curable molding is selected from lower group: silicone oil, silicones, modified resin, or its combination.
In another preference, described curing molding includes: at 100～140 DEG C, heat treatment makes described preform de-bubbled, then heat treatment 1-5h at 160～200 DEG C, heat treatment 0.5-3h at 210～250 DEG C, then be warming up at 250～350 DEG C and proceed heat treatment 1-5h.
In another preference, refractive index >=1.50 of described cured product, it is preferred that >=1.55.
In another preference, the described cured product 5% thermal weight loss temperature in nitrogen is >=450 DEG C, it is preferred that for >=480 DEG C.
In another preference, the described cured product 5% thermal weight loss temperature in nitrogen is 475～600 DEG C, it is preferred that be 480～550 DEG C.
In another preference, the described cured product 1000 DEG C of residual volumes in nitrogen are >=60%, it is preferred that for >=65%.
In another preference, the described cured product 1000 DEG C of residual volumes in nitrogen are 60～85%, it is preferred that be 65～80%.
In another preference, the dielectric constant < 3.0 of described cured product, it is preferred that for < 2.8；It is more preferably 2.5-2.8.
In another preference, the dielectric loss of described cured product is 2～8 × 10-3。
In another preference, the dielectric loss of described cured product is 2.5～3.6 × 10-3。
In another preference, described curing molding is the molding that is heating and curing；It is preferred that described curing molding temperature is 100～350 DEG C.
In another preference, described method includes step: with organic siliconresin as described in the first aspect of the invention individually or blended with the performed polymer of other optional curable molding after be shaped, obtain preform；
It is heated described preform solidifying, obtains described goods.
In another preference, described curing molding includes: at 100～140 DEG C, heat treatment makes described preform de-bubbled, then heat treatment 1-5h at 160～200 DEG C, heat treatment 0.5-3h at 210～250 DEG C, then be warming up at 250～350 DEG C and proceed heat treatment 1-5h.
In another preference, described molding is to be undertaken by the moulding process selected from lower group: fill mould, solution spin coating, or solution drop coating.
In another preference, described solution spin coating or solution drop coating include step: individually or be dissolved in organic solvent wiring solution-forming with the performed polymers of other optional curable molding by organic siliconresin as described in the first aspect of the invention, then carry out spin coating or drop coating；Preferably, described solvent is selected from lower group: described organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, chloroform, acetone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, or its combination.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme.As space is limited, this is no longer going to repeat them.
Detailed description of the invention
The present inventor is through long-term and deep research, it is surprised to find that, copolymerization is carried out with the silane monomer containing benzocyclobutene and other silane monomers, can obtain that there is good heat stability, the organosilicon material of low-k and high refractive index, it is possible to be used as high-performance resin matrix or encapsulating material.Based on above-mentioned discovery, inventor completes the present invention.
Term
Term " alkyl of C1～C4 " refers to the straight or branched alkyl with 1～4 carbon atom, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, or similar group.
Term " C1～C4 haloalkyl " refers to have 1～4 carbon atom, and the straight or branched alkyl that at least one hydrogen atom is optionally substituted by halogen, such as trifluoro propyl, or similar group.
Term " C2～C4 thiazolinyl " refers to the straight or branched thiazolinyl with 2～4 carbon atoms, such as vinyl, acrylic, pi-allyl, 1-butylene base, crotyl, or similar group.
Term " C1～C4 alkoxyl " refers to have the substituent group that the straight or branched alkyl of 1～4 carbon atom is connected to form with oxygen, such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, or similar group.
Term " alkyl of C8～C17 " refers to the straight or branched alkyl with 8～17 carbon atoms, such as decyl, 2,2-dimethyl octyl groups, dodecyl, pentadecyl, or similar group.
Term " C6～C10 aryl " refers to the aryl with 6～10 carbon atoms, including monocycle or aryl bicyclic, for instance phenyl, naphthyl, or similar group.
Term " heteroaryl of C1～C10 " refers to have 1-10 carbon atom, and has one or more heteroatomic aryl in ring system, such as pyridine radicals, thienyl, piperidyl, or similar group.
Term " halogen " refers to fluorine, chlorine, bromine or iodine.
Organic siliconresin containing benzocyclobutane thiazolinyl
A kind of organic siliconresin containing benzocyclobutane thiazolinyl, it is characterised in that described organic siliconresin is to prepare with the copolymerization that is hydrolyzed of the such as monomer shown in following formula A and the optional monomer as shown in following formula B:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
More preferably, described formula A monomer is chosen from the monomer of lower group (a):
(a) benzocyclobutane thiazolinyl trimethoxy silane, benzocyclobutene ethyl triethoxy silicane alkane, benzocyclobutane thiazolinyl trichlorosilane, phenyl (benzocyclobutane thiazolinyl) dimethoxysilane, phenyl (benzocyclobutane thiazolinyl) diethoxy silane, phenyl (benzocyclobutane thiazolinyl) dichlorosilane, dibenzo cyclobutane base dimethoxysilane, dimethyl (benzocyclobutane thiazolinyl) Ethoxysilane, methyl (benzocyclobutane thiazolinyl) dimethoxysilane, methyl (benzocyclobutane thiazolinyl) diethoxy silane, methyl (benzocyclobutane thiazolinyl) dichlorosilane, vinyl (benzocyclobutane thiazolinyl) dimethoxysilane, vinyl (benzocyclobutane thiazolinyl) diethoxy silane, vinyl (benzocyclobutane thiazolinyl) dichlorosilane, dimethylbiphenyl cyclobutane methoxylsilane；
And described formula B monomer is chosen from the monomer of lower group (b):
(b) phenyl triethoxysilane, phenyltrimethoxysila,e, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, methyl vinyl diethoxysilane, methyl trifluoro propyl diethoxy silane, trimethylethoxysilane, dodecyltrimethoxysilane, tetraethyl orthosilicate, or its combination.
Wherein, each monomer can be single functionality, bifunctionality or three-functionality-degree, and in another preference, in described formula A, having at least (being preferably a 1-3) R is C1～C4 alkoxyl.
In another preference, in described formula B, having at least (being preferably a 1-4) R is C1～C4 alkoxyl.
In another preference, in described formula A, each R is each independently selected from lower group: C1～C4 alkyl, C2～C4 thiazolinyl, C1～C4 alkoxyl.
In another preference, in described formula B, each R is each independently selected from lower group: C1～C4 alkyl, C1～C4 alkoxyl, phenyl.
The consumption of each monomer has no particular limits, it is preferable that in the monomer that described hydrolysis copolymerization uses:
The molfraction a of formula A1 monomer is 0≤a≤0.8, and wherein, described formula A1 monomer has the structure shown in formula A, and in described formula A, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction b of formula A2 monomer is 0≤b≤0.6, and wherein, described formula A2 monomer has the structure shown in formula A, and in described formula A, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction c of formula A3 monomer is 0≤c≤0.3, and wherein, described formula A3 monomer has the structure shown in formula A, and in described formula A, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction d of formula B1 monomer is 0≤d≤0.3, and wherein, described formula B1 monomer has the structure shown in formula B, and in described formula B, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction e of formula B2 monomer is 0≤e≤0.5, and wherein, described formula B2 monomer has the structure shown in formula B, and in described formula B, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction f of formula B3 monomer is 0≤f≤0.4, and wherein, described formula B3 monomer has the structure shown in formula B, and in described formula B, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction g of formula B4 monomer is 0 < g≤0.3, and wherein, described formula B4 monomer has the structure shown in formula B, and in described formula B, has the group that 4 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
And be 0 during a, b, c difference.
In another preference, described organic siliconresin has average composition formula shown in formula I:
Wherein, a+b+c+d+e+f+g=1, and R1、R2、R3、R4、R5、R6、R7、R8Or R9It is independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, aromatic radical, C8～C17 alkyl；It is preferred that R1、R2、R3、R4、R5、R6、R7、R8Or R9It is independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, dodecyl；
And the span of a, b, c, d, e, f, g is as follows: 0≤a≤0.8,0≤b≤0.6,0≤c≤0.3,0≤d≤0.3,0≤e≤0.5,0≤f≤0.4,0 < g≤0.3.
And be 0 during a, b, c difference.
In another preference, described organic siliconresin molecular weight is 1000-20000.
In atent solvent, it is hydrolyzed polymerization with the such as monomer shown in following formula A and the optional monomer as shown in following formula B, obtains described organic siliconresin:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, benzocyclobutane thiazolinyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
It is preferred that in described formula A, have at least a R (being preferably 1,2 or 3) not for benzocyclobutane thiazolinyl；And in described formula B, each R is not all benzocyclobutane thiazolinyl.
Preferably, described method includes step:
In atent solvent, with the silane monomer containing benzocyclobutane thiazolinyl selected from lower group (a) be hydrolyzed polymerization selected from the silane monomer of lower group (b), obtain organic siliconresin shown in formula I:
Wherein, X is independently selected from methoxyl group, ethyoxyl, chlorine, bromine；R1、R2、R3、R4、R5、 R6、R7、R8Or R9It is independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, aromatic radical, C8～C17 alkyl；It is preferred that R1、R2、R3、R4、R5、R6、R7、R8Or R9It is independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, dodecyl；
Group (a) for a kind of containing benzocyclobutene silane or the multiple combination containing benzocyclobutene silane；
The combination that group (b) is one or more silane.
Described hydrolytic-polymeric reaction preferably carries out under acidic catalyst and/or water exist；It is preferred that described acidic catalyst is selected from lower group: hydrochloric acid, sulphuric acid, acetic acid, formic acid, or its combination.
The mol ratio of monomer, acid catalyst and water is preferably 1:0.2～20:0～10.
Described atent solvent has no particular limits, it is preferred that selected from lower group: benzene,toluene,xylene, trimethylbenzene, or its combination.
In another preference, described reaction temperature is 0～130 DEG C.
In another preference, the described response time is 3～35 hours.
The concrete grammar of described hydrolytic polymerization has no particular limits, in a preferred embodiment of the invention, described method includes: at 0～30 DEG C, the mixed solution of dropping group (a) monomer and group (b) monomer in the atent solvent be dissolved with acidic catalyst and water, then rises to and continues reaction at 70～130 DEG C.
In another preference, described method also includes: after dropwising, and after reacting a period of time, rises to and continues reaction at 70～130 DEG C at 10～30 DEG C.
In another preference, described method also includes: after dropwising, and after reacting 1-5h, rises to and continues reaction 3-24h at 70～130 DEG C at 10～30 DEG C.
Cured product containing benzocyclobutane thiazolinyl unit
Present invention also offers a kind of cured product, described cured product be with the organic siliconresin containing benzocyclobutane thiazolinyl of the present invention individually or with the performed polymer of other curable molding blended after carry out curing molding and prepare.
Wherein, the performed polymer of other described curable molding has no particular limits, can be selected for any resin or organic molecule that can jointly carry out with described organic siliconresin and solidifying, for instance resin containing unsaturated bond (not including aromatic ring) or organic molecule.In a preferred embodiment of the invention, the performed polymer of the curable molding of described other is selected from lower group: silicone oil, silicones or other modified resin.
Described curing molding has no particular limits, it is possible to be the resin curing molding method of this area routine, for instance, in a preference of the present invention, described curing molding is the molding that is heating and curing.Preferably, described curing molding temperature is 100～350 DEG C.
In another preference, described cured product adopts following method to prepare:
With the organic siliconresin containing benzocyclobutane thiazolinyl of the present invention individually or with the performed polymer of other optional curable molding blended after be shaped, obtain preform；
It is heated described preform solidifying, obtains described goods.
In another preference, described curing molding includes: at 100～140 DEG C, heat treatment makes described preform de-bubbled, then heat treatment 1-5h at 160～200 DEG C, heat treatment 0.5-3h at 210～250 DEG C, then be warming up at 250～350 DEG C and proceed heat treatment 1-5h.
In another preference, described molding is to be undertaken by the moulding process selected from lower group: fill mould, solution spin coating, or solution drop coating.
In another preference, described solution spin coating or solution drop coating include step: be dissolved in organic solvent by the performed polymer of organic siliconresin as described in the first aspect of the invention and other optional curable molding wiring solution-forming, then carry out spin coating or drop coating；Preferably, described solvent is selected from lower group: described organic solvent is toluene, dimethylbenzene, trimethylbenzene, diphenyl ether, Ketohexamethylene, chloroform, acetone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, or its combination.
The major advantage of the present invention:
(1) the organic silicon monomer preparation process containing benzocyclobutene provided by the present invention is simple, compare with the organosiloxane monomer containing benzocyclobutene reported in prior art, synthesize and can complete preparation only with simple grignard reaction, and the raw material sources that use are extensive, silane and halo benzocyclobutene are marketable material, and reaction yield is higher.
(2) organic siliconresin of the present invention adopts hydrolytic polymerization just can be prepared, relative in prior art, the preparation of the prepolymer of monomer needs to carry out at relatively high temperatures, preparation method is simple, mild condition, react controlled, and the molecular weight viscosity of the prepolymer obtained can efficiently control, and has good film property, caking property and processability.
(3) organic siliconresin of the present invention is without using noble metal catalyst such as platinum etc. to be prepared, and significantly reduces the cost of preparation.
(4) preparation method of the present invention is simple, and equipment requirements is low, is suitable for industrialized production.
(5) organic siliconresin provided by the present invention is for preparing the cured product with good electric property, heat resistance and mechanical property, and its heat stability is significantly improved.There is after thermally treated solidification high temperature tolerance (5% thermal weight loss temperature is up to 496 DEG C), good dielectric properties (dielectric constant is up to 2.71) and higher index of refraction (n is 1.56) etc., it is a kind of new type high temperature cured silicone resin, there is the prospect being used as high-performance resin matrix or encapsulating material in fields such as being applied to large scale integrated circuit, microelectronics industry, electrical equipment and Aero-Space.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition, or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.
The preparation of embodiment 1 benzyl ring butylene triethoxysilane
Under argon shield; magnesium chips (10.8g is added in the dry three-necked bottle of 500mL; 0.45mol); tetraethyl orthosilicate (104g; 0.5mol); anhydrous tetrahydro furan 50mL; 4-bromine benzocyclobutene (36.6g is slowly dripped under room temperature; 40mL anhydrous tetrahydrofuran solution 0.2mol), injects 100mL dry toluene after dripping complete being stirred at room temperature 3 hours, and a large amount of solids precipitate out; filtration is desalted; rotation is evaporated off the decompression distillation of low boiling point solvent rear pump or output pump: collects 155-165 DEG C of (1.5mmHg) fraction, obtains water white transparency shape liquid 32.45g, yield 61%.
Hydrogen stave is levied1HNMR(CDCl3, 400MHz): 1.26～1.30 (t, 9H), 3.23 (s, 6H), 3.82～3.88 (m, 4H), 7.11～7.13 (d, 1H), 7.38 (s, 1H), 7.52～7.54 (d, 2H).
The preparation of embodiment 2 methyl (benzocyclobutane thiazolinyl) dichlorosilane
Under argon shield; magnesium chips (9.6g is added in the dry three-necked bottle of 500mL; 0.4mol); methyl trichlorosilane (75g; 0.5mol); anhydrous tetrahydro furan 50mL; 4-bromine benzocyclobutene (36.6g is slowly dripped under room temperature; 40mL anhydrous tetrahydrofuran solution 0.2mol), injects 80mL dry toluene after dripping complete being stirred at room temperature 3 hours, and a large amount of solids precipitate out; filtration is desalted; rotation is evaporated off the decompression distillation of low boiling point solvent rear pump or output pump: collects 96-106 DEG C of (1.5mmHg) fraction, obtains water white transparency shape liquid 22.46g, yield 52%.
Hydrogen stave is levied1HNMR(CDCl3, 400MHz): 0.38 (s, 3H), 3.82～3.88 (m, 4H), 7.11～7.13 (d, 1H), 7.38 (s, 1H), 7.52～7.54 (d, 2H).
Embodiment 3 is containing the preparation of benzyl ring cyclobutenyl organic siliconresin I
null500 milliliters of clean there-necked flasks add 60 milliliters of water、60 milliliters of concentrated hydrochloric acid and 30 milliliters of toluene，It is stirred vigorously down and drips 5.2 grams of tetraethyl orthosilicates by constant pressure funnel、39.6 gram phenyltrimethoxysila,e、18.2 gram aminomethyl phenyl dimethoxysilane、22.0 gram vinyl (benzocyclobutane thiazolinyl) dimethoxysilane、22.4 the mixed solution of gram benzocyclobutane thiazolinyl trimethoxy silane and 30 milliliters of toluene，Reaction temperature controls below 20 DEG C，Reaction 3h is continued after dropwising，It is subsequently heated and continues to react 3h to 80 DEG C，It is cooled to room temperature，It is washed to neutrality，Organic over anhydrous dried over sodium sulfate，Toluene is removed after filtration，Decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound，Obtain 26.2 grams containing benzocyclobutane thiazolinyl organic siliconresin I.
Embodiment 4 is containing the preparation of benzocyclobutane thiazolinyl organic siliconresin II
500 milliliters of clean there-necked flasks add 80 milliliters of acetic acid and 30 milliliters of toluene, it is stirred vigorously down and drips 5.0 grams of tetraethyl orthosilicates by constant pressure funnel, 42.5 gram phenyl triethoxysilane, 19.8 gram methyl (benzocyclobutane thiazolinyl) diethoxy silane, 12.5 gram benzocyclobutane thiazolinyl trimethoxy silane, the mixed solution of 3.6 grams of dimethyl (benzocyclobutane thiazolinyl) Ethoxysilanes and 20 milliliters of toluene, reaction temperature controls below 20 DEG C, dropwise post-heating and continue reaction 16h to 100 DEG C, it is cooled to room temperature, it is washed to neutrality, organic over anhydrous dried over sodium sulfate, toluene is removed after filtration, decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound, obtain 22.7 grams containing benzocyclobutane thiazolinyl organic siliconresin II.
Embodiment 5 is containing the preparation of benzocyclobutane thiazolinyl organic siliconresin III
500 milliliters of clean there-necked flasks add 15 milliliters of water, 50 milliliters of acetic acid and 30 milliliters of toluene, it is stirred vigorously down and drips 3.8 grams of tetraethyl orthosilicates by constant pressure funnel, 33.2 gram phenyl triethoxysilane, 21.8 gram aminomethyl phenyl dimethoxysilane, 11.2 the mixed solution of gram benzocyclobutene ethyl triethoxy silicane alkane and 20 milliliters of toluene, reaction temperature controls below 20 DEG C, dropwise post-heating and continue reaction 15h to 110 DEG C, it is cooled to room temperature, it is washed to neutrality, organic over anhydrous dried over sodium sulfate, toluene is removed after filtration, decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound, obtain 19.1 grams containing benzocyclobutane thiazolinyl organic siliconresin III.
The preparation of the embodiment 6 organic siliconresin IV containing benzocyclobutane thiazolinyl
null250 milliliters of clean there-necked flasks add 25 milliliters of water、25 milliliters of concentrated hydrochloric acid and 30 milliliters of toluene，It is stirred vigorously down and drips 4.0 grams of tetraethyl orthosilicates by constant pressure funnel、42.5 gram phenyl triethoxysilane、29.8 gram phenyl (benzocyclobutane thiazolinyl) dimethoxysilane、11.8 gram methyl (benzocyclobutane thiazolinyl) dimethoxysilane、16.2 the mixed solution of gram benzocyclobutane thiazolinyl trimethoxy silane and 20 milliliters of toluene，Reaction temperature controls below 20 DEG C，Reaction 3h is continued after dropwising，It is subsequently heated and continues to react 5h to 80 DEG C，It is cooled to room temperature，It is washed to neutrality，Organic over anhydrous dried over sodium sulfate，Toluene is removed after filtration，Decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound，Obtain 21.3 grams containing benzocyclobutane thiazolinyl organic siliconresin IV.
The preparation of the embodiment 7 organic siliconresin V containing benzocyclobutane thiazolinyl
null250 milliliters of clean there-necked flasks add 80 milliliters of acetic acid and 20 milliliters of dimethylbenzene，It is stirred vigorously down and drips 4.0 grams of tetraethyl orthosilicates by constant pressure funnel、24.1 gram phenyl triethoxysilane、11.32 gram diphenyl diethoxy silane、1.2 grams of trimethylethoxysilanes、35.4 gram methyl (benzocyclobutane thiazolinyl) dimethoxysilane、11.5 the mixed solution of gram benzocyclobutane thiazolinyl trimethoxy silane and 20 milliliters of dimethylbenzene，Reaction temperature controls below 20 DEG C，Dropwise post-heating and continue reaction 16h to 130 DEG C，It is cooled to room temperature，It is washed to neutrality，Organic over anhydrous dried over sodium sulfate，Toluene is removed after filtration，Decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound，Obtain 19.6 grams containing benzocyclobutane thiazolinyl organic siliconresin V.
The preparation of the embodiment 8 organic siliconresin VI containing benzocyclobutane thiazolinyl
null250 milliliters of clean there-necked flasks add 25 milliliters of water、25 milliliters of concentrated hydrochloric acid and 20 milliliters of toluene，It is stirred vigorously down and drips 4.0 grams of tetraethyl orthosilicates by constant pressure funnel、29.2 gram dodecyltrimethoxysilane、18.2 gram aminomethyl phenyl dimethoxysilane、22.0 gram vinyl (benzocyclobutane thiazolinyl) dimethoxysilane、11.2 gram benzocyclobutane thiazolinyl trimethoxy silane、The mixed solution of 4.8 grams of dimethylbiphenyl cyclobutane methoxylsilanes and 20 milliliters of toluene，Reaction temperature controls below 20 DEG C，Reaction 3h is continued after dropwising，It is subsequently heated and continues to react 5h to 80 DEG C，It is cooled to room temperature，It is washed to neutrality，Organic over anhydrous dried over sodium sulfate，Toluene is removed after filtration，Decompression is warmed up to 150 DEG C/10mba and sloughs micromolecular compound，Obtain 23.3 grams containing benzocyclobutane thiazolinyl organic siliconresin VI.
The solidification of the embodiment 9 organic siliconresin I containing benzocyclobutane thiazolinyl
The organic siliconresin I containing benzocyclobutane thiazolinyl taking 2.0 grams of embodiment 3 preparations is cast in mould, 120 DEG C of heat treatments 1 hour, vacuum outgas is steeped, and then proceedes to heat up 180 DEG C of heat treatments 3 hours, 230 DEG C of heat treatments 1 hour, 300 DEG C of heat treatments can obtain highly cross-linked organic siliconresin in 2 hours.
Gained sample TGA tests its heat stability, and carrier gas used is nitrogen, and heating rate is 10 DEG C/min；Agilent impedance instrument 4294A tests its dielectric properties；Ellipsometer tests its index of refraction.
The all documents mentioned in the present invention are incorporated as reference all in this application, are individually recited as reference such just as each section of document.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.
Claims (10)
1. the organic siliconresin containing benzocyclobutane thiazolinyl, it is characterised in that described organic siliconresin is to prepare with the copolymerization that is hydrolyzed of the such as monomer shown in following formula A and the optional monomer as shown in following formula B:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, benzocyclobutane thiazolinyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
It is preferred that in described formula A, have at least a R not for benzocyclobutane thiazolinyl；And in described formula B, each R is not all benzocyclobutane thiazolinyl；
More preferably, described formula A monomer is chosen from the monomer of lower group (a):
(a) benzocyclobutane thiazolinyl trimethoxy silane, benzocyclobutene ethyl triethoxy silicane alkane, benzocyclobutane thiazolinyl trichlorosilane, phenyl (benzocyclobutane thiazolinyl) dimethoxysilane, phenyl (benzocyclobutane thiazolinyl) diethoxy silane, phenyl (benzocyclobutane thiazolinyl) dichlorosilane, dibenzo cyclobutane base dimethoxysilane, dimethyl (benzocyclobutane thiazolinyl) Ethoxysilane, methyl (benzocyclobutane thiazolinyl) dimethoxysilane, methyl (benzocyclobutane thiazolinyl) diethoxy silane, methyl (benzocyclobutane thiazolinyl) dichlorosilane, vinyl (benzocyclobutane thiazolinyl) dimethoxysilane, vinyl (benzocyclobutane thiazolinyl) diethoxy silane, vinyl (benzocyclobutane thiazolinyl) dichlorosilane, dimethylbiphenyl cyclobutane methoxylsilane, or its combination；
And described formula B monomer is chosen from the monomer of lower group (b):
(b) phenyl triethoxysilane, phenyltrimethoxysila,e, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, trimethylethoxysilane, methyl vinyl diethoxysilane, methyl trifluoro propyl diethoxy silane, dodecyltrimethoxysilane, tetraethyl orthosilicate, or its combination.
2. organic siliconresin as claimed in claim 1, it is characterised in that in the monomer that described hydrolysis copolymerization uses:
The molfraction a of formula A1 monomer is 0≤a≤0.8, and wherein, described formula A1 monomer has the structure shown in formula A, and in described formula A, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction b of formula A2 monomer is 0≤b≤0.6, and wherein, described formula A2 monomer has the structure shown in formula A, and in described formula A, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction c of formula A3 monomer is 0≤c≤0.3, and wherein, described formula A3 monomer has the structure shown in formula A, and in described formula A, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction d of formula B1 monomer is 0≤d≤0.3, and wherein, described formula B1 monomer has the structure shown in formula B, and in described formula B, has the group that 1 R base is chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction e of formula B2 monomer is 0≤e≤0.5, and wherein, described formula B2 monomer has the structure shown in formula B, and in described formula B, has the group that 2 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction f of formula B3 monomer is 0≤f≤0.4, and wherein, described formula B3 monomer has the structure shown in formula B, and in described formula B, has the group that 3 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
The molfraction g of formula B4 monomer is 0 < g≤0.3, and wherein, described formula B4 monomer has the structure shown in formula B, and in described formula B, has the group that 4 R bases are chosen from lower group: C1～C4 alkoxyl, halogen；
And be 0 during a, b, c difference；
It is preferred that described organic siliconresin molecular weight is 1000-20000.
3. the preparation method of organic siliconresin as claimed in claim 1, it is characterised in that include step:
In atent solvent, it is hydrolyzed polymerization with the such as monomer shown in following formula A and the optional monomer as shown in following formula B, obtains described organic siliconresin:
In formula, each R is each independently selected from lower group: hydrogen, C1～C4 alkyl, C1～C4 alkoxyl, C1～C4 haloalkyl, C2～C4 thiazolinyl, C6～C10 aryl, the heteroaryl of C1～C10, C8～C17 alkyl, halogen；It is preferred that each R is each independently selected from lower group: methyl, ethyl, propyl group, trifluoro propyl, vinyl, phenyl, benzocyclobutane thiazolinyl, dodecyl, methoxyl group, ethyoxyl, chlorine, bromine；
And in described formula A, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
And in described formula B, have at least the R group being chosen from lower group: C1～C4 alkoxyl, halogen；
It is preferred that in described formula A, have at least a R not for benzocyclobutane thiazolinyl；And in described formula B, each R is not all benzocyclobutane thiazolinyl；
Preferably, described method includes step:
In atent solvent, with the silane monomer containing benzocyclobutane thiazolinyl selected from lower group (a) be hydrolyzed polymerization selected from the silane monomer of lower group (b), obtain organic siliconresin as claimed in claim 1:
(a) benzocyclobutane thiazolinyl trimethoxy silane, benzocyclobutene ethyl triethoxy silicane alkane, benzocyclobutane thiazolinyl trichlorosilane, phenyl (benzocyclobutane thiazolinyl) dimethoxysilane, phenyl (benzocyclobutane thiazolinyl) diethoxy silane, phenyl (benzocyclobutane thiazolinyl) dichlorosilane, dibenzo cyclobutane base dimethoxysilane, dimethyl (benzocyclobutane thiazolinyl) Ethoxysilane, methyl (benzocyclobutane thiazolinyl) dimethoxysilane, methyl (benzocyclobutane thiazolinyl) diethoxy silane, methyl (benzocyclobutane thiazolinyl) dichlorosilane, vinyl (benzocyclobutane thiazolinyl) dimethoxysilane, vinyl (benzocyclobutane thiazolinyl) diethoxy silane, vinyl (benzocyclobutane thiazolinyl) dichlorosilane, dimethylbiphenyl cyclobutane methoxylsilane, or its combination；
(b) phenyl triethoxysilane, phenyltrimethoxysila,e, diphenyl diethoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, dichloromethyl phenylsilane, aminomethyl phenyl diethoxy silane, methyl vinyl diethoxysilane, methyl trifluoro propyl diethoxy silane, trimethylethoxysilane, dodecyltrimethoxysilane, tetraethyl orthosilicate, or its combination.
4. method as claimed in claim 3, it is characterised in that described hydrolytic-polymeric reaction carries out under acidic catalyst and/or water exist.
5. method as claimed in claim 4, it is characterised in that described acidic catalyst is selected from lower group: hydrochloric acid, sulphuric acid, acetic acid, formic acid, or its combination.
6. method as claimed in claim 3, it is characterised in that described atent solvent is selected from lower group: benzene,toluene,xylene, trimethylbenzene, or its combination.
7. method as claimed in claim 3, it is characterised in that described method includes: at 0～30 DEG C, drips the mixed solution of formula A monomer and formula B monomer in the solvent be dissolved with acidic catalyst；
To, at the solution warms after described dropwising to 70～130 DEG C, continuing reaction.
8. a cured product, it is characterised in that described cured product be with organic siliconresin as claimed in claim 1 individually or with the performed polymer of other curable molding blended after carry out curing molding and prepare.
9. cured product as claimed in claim 8, it is characterised in that described curing molding is the molding that is heating and curing；It is preferred that described curing molding temperature is 100～350 DEG C.
10. the preparation method of cured product as claimed in claim 8, it is characterized in that, described method includes step: with organic siliconresin as claimed in claim 1 individually or with the performed polymer of other optional curable molding blended after be shaped, obtain preform；
It is heated described preform solidifying, obtains described goods.
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| CN106866722A (en) * | 2017-01-12 | 2017-06-20 | 复旦大学 | A kind of organo-silicon compound containing benzocyclobutene functionalization and preparation method thereof |
| CN108586748A (en) * | 2018-04-23 | 2018-09-28 | 复旦大学 | A kind of benzocyclobutene functionalization organosilicon polymer and its preparation method and application |
| CN114479087A (en) * | 2022-03-14 | 2022-05-13 | 中国科学院化学研究所 | Benzocyclobutene functionalized polysiloxane and preparation method thereof |
| CN114995061A (en) * | 2022-08-01 | 2022-09-02 | 明士(北京)新材料开发有限公司 | Low-water-absorption positive photosensitive resin composition and preparation method and application thereof |
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| CN114995061A (en) * | 2022-08-01 | 2022-09-02 | 明士(北京)新材料开发有限公司 | Low-water-absorption positive photosensitive resin composition and preparation method and application thereof |
| CN114995061B (en) * | 2022-08-01 | 2022-11-01 | 明士(北京)新材料开发有限公司 | Low-water-absorption positive photosensitive resin composition and preparation method and application thereof |
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