CN117903342A - Thermally crosslinkable polymer with high frequency and low dielectric constant, and preparation method and application thereof - Google Patents

Thermally crosslinkable polymer with high frequency and low dielectric constant, and preparation method and application thereof Download PDF

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Publication number
CN117903342A
CN117903342A CN202410076271.9A CN202410076271A CN117903342A CN 117903342 A CN117903342 A CN 117903342A CN 202410076271 A CN202410076271 A CN 202410076271A CN 117903342 A CN117903342 A CN 117903342A
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alkyl
alkynyl
alkenyl
halogenated
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房强
黄港
孙晶
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a thermally crosslinkable modified polymer with high frequency and low dielectric constant, and a synthesis method and application thereof. Specifically, the invention provides a heat-curable modified polymer which has a monomer structure shown in the following formula I, wherein the definition of each group is as described in the specification. The heat-curable modified polymer can be used as a low dielectric constant matrix resin or packaging material and can be widely applied to the fields of high-frequency communication, microelectronics industry, aerospace and the like.

Description

Thermally crosslinkable polymer with high frequency and low dielectric constant, and preparation method and application thereof
Technical Field
The invention relates to the field of thermosetting polyolefin materials, in particular to a thermally crosslinkable polymer, a preparation method thereof and application thereof as a high-frequency low-dielectric constant material.
Background
With the rapid development of internet of things (IoT) and high-frequency communication (5G), the transmission speed and transmission quality of electronic signals need to meet higher requirements. Compared with the fourth generation mobile communication (4G), the 5G has the characteristics of high signal transmission speed (about 10 Gbps), small signal delay (1 ms) and multi-terminal access. In order to realize high-speed and high-capacity signal transmission, the 5G communication technology mainly adopts sub-6 GHz and millimeter wave frequency bands for signal transmission, and the high transmission frequency can lead a circuit to generate obvious skin effect and ionization loss, so that a base material heats to increase signal loss and energy dissipation, thereby influencing the signal transmission quality. Signal transmission losses in digital circuits mainly include conductor loss (T LC) and dielectric loss (T LD), whereas dielectric loss T LD has the following relationship with the dielectric constant (D k) and dielectric loss (D f) of the dielectric material: k represents a coefficient; f represents frequency; c represents the speed of light. The dielectric constants of the low dielectric substrate materials commonly used at present are not too large (2.0-3.5), but the dielectric losses are different in magnitude (10 -2～10-4), so that the dielectric losses of the low dielectric materials have more important influence on high-frequency and high-speed circuits.
In view of the foregoing, there is a need in the art to develop low dielectric materials that meet the ultra-low dielectric loss (< 10 -4) while having excellent mechanical properties and processability.
Disclosure of Invention
An object of the present invention is to provide a low dielectric material having a low dielectric constant and an ultra-low dielectric loss while having excellent mechanical properties and processability, and a method for preparing the same.
It is another object of the present invention to provide a heat cured product having a low dielectric constant and ultra low dielectric loss and its use.
In a first aspect of the present invention, there is provided a curable modified polymer having a monomer structure of formula I:
wherein,
N 1、n2 satisfies n 1：(n1+n2) = (0.01 to 1): 1;
n 1、n2、n3 satisfies n 1:(n1+n2+n3) = (0.01 to 1): 1, a step of;
n 4 is an integer from 0 to 12;
Each R 1 and R 2 is independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido (-N=O-) cyanate (-N=O-;
R 3、R4 and R 5 are each independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy a 5-10 membered heteroaryl group having 1 to 3 heteroatoms each independently selected from N, O and S, a benzo 5-6 membered heterocyclyl group, a benzo C3-6 cycloalkyl group, a benzo C4-6 cycloalkenyl group, a benzo C4-6 cycloalkynyl group, a C1-C6 hydroxyalkyl group, a C2-C6 hydroxyalkenyl group, a C2-C6 hydroxyalkynyl group, a hydroxyphenyl group (-Ph-OH), a ureido group, an amino ester group, -CO-NH- (C1-C4 alkyl) an isocyanate group (-n=c=o), a cyanate group (-O-CN);
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), phenyl ether (Ph-O-), phenyl sulfide (Ph-S-), C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, isocyanate group, cyanate group;
wherein the monomer structure shown in the formula I contains m unsaturated degrees, and m is 2-10;
or in the monomer structure shown in the formula I Comprising p crosslinkable groups or linkages, p being from 1 to 10, wherein said crosslinkable groups or linkages are selected from the group consisting of: cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), carbamate (-O-C (O) -NH-), ureido (-NH-C (O) -NH-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-C (O) O-), alkenyl, alkynyl, phenyl, heterocyclyl, cycloalkenyl, cycloalkynyl, isocyanate, cyanate.
In another preferred embodiment, the alkyl, alkenyl, alkynyl groups are straight or branched.
In another preferred embodiment, n 4 is an integer from 0 to 5; preferably 0-2.
In another preferred embodiment, the halogen is fluorine.
In another preferred embodiment, R 1、R2 are the same or different, preferably the same.
In another preferred embodiment, R 3、R4 are the same or different, preferably the same.
In another preferred embodiment, n 2 = 0.
In another preferred embodiment, n 3 = 0.
In another preferred embodiment, the curing is thermally curable.
In another preferred embodiment, n4 is 0,
R 3、R4 are each independently selected from the group consisting of: H. C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 hydroxyalkyl, phenyl, halogenated C1-C6 alkyl-substituted phenyl;
R 5 is a group containing a crosslinkable group or bond selected from the group; H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkynyl, C2-C6 hydroxyphenyl, ureido, C1- (C4-NH) isocyanate, isocyanate;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), phenyl ether (Ph-O-), phenyl sulfide (Ph-S-), C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl;
Preferably, R 5 is a group selected from the group consisting of a crosslinkable group or a bond; H. a substituted or unsubstituted group selected from the group consisting of: C2-C6 alkenyl, C2-C6 alkynyl, C6 aryl, C1-C6 alkoxy, C6 aryloxy, 5-6 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, hydroxyphenyl;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano, hydroxy, mercapto, amino, carboxyl, phenyl ether, phenyl sulfide, C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, -CO-NH- (C1-C4 alkyl);
Wherein R 3 is selected from the group consisting of:
Preferably, R 5 is a group selected from the group consisting of: vinyl, styryl, ethynyl, phenylethynyl, benzocyclobutenyl, vinylbenzocyclobutenyl, trifluorovinylphenyl ether, cyano, epoxy, cyanate, isocyanate groups.
In another preferred embodiment, each R 1、R2、R3、R4 is independently selected from the group consisting of: H. C1-C4 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 hydroxyalkyl, phenyl, halogenated C1-C4 alkyl-substituted phenyl.
In another preferred embodiment, each R 1、R2、R3、R4 is independently selected from the group consisting of: methyl, ethyl, propyl, trifluoropropyl, phenyl, 4-trifluoromethylphenyl, 3, 5-bistrifluoromethylphenyl.
In another preferred embodiment, n 1、n2 satisfies n 1：(n1+n2) is (0.3 to 1): 1; preferably (0.3-0.6): 1.
In another preferred embodiment, R 3 and R 4 are both methyl, and R5 is
In another preferred embodiment, R 3 and R 4 are both methyl, and R5 is
In another preferred embodiment, R 3 and R 4 are both methyl, and R 5 is
In another preferred embodiment, each substituent is a specific group corresponding to the compounds in the examples.
In another preferred embodiment, the modified polymer has a monomer structure selected from the group consisting of:
In a second aspect of the present invention, there is provided a method for producing a modified polymer according to the first aspect of the present invention, comprising the steps of:
reacting a polymer shown in the following formula (II) with a silane compound/siloxane compound containing a crosslinkable group shown in the formula (III) in an inert solvent under the action of a catalyst to obtain a modified polymer shown in the formula (I);
wherein,
N 0 is 1 to 2000, and n 0 and n 3 satisfy n 0：(n0+n3) = (0.01 to 1): 1, a step of;
n 4 is an integer from 0 to 12;
Each R 1 and R 2 is independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido (-N=O-) cyanate (-N=O-;
R 3、R4 and R 5 are each independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1 to 3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkynyl, C2-C6 hydroxyphenyl (-hydroxy-phenyl), ureido, C4-alkyl-CO- (C4-OH), isocyanate;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano, hydroxy, mercapto, amino, carboxyl, phenyl ether, phenyl sulfide, C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-C6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano, hydroxy, mercapto, amino, carboxyl, C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, isocyanate group, cyanate group;
wherein the monomer structure shown in the formula I contains m unsaturated degrees, and m is 2-10;
or in the monomer structure shown in the formula I Comprising p crosslinkable groups or linkages, p being from 1 to 10, wherein said crosslinkable groups or linkages are selected from the group consisting of: cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), carbamate (-O-C (O) -NH-), ureido (-NH-C (O) -NH-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-C (O) O-), alkenyl, alkynyl, phenyl, heterocyclyl, cycloalkenyl, cycloalkynyl, isocyanate, cyanate.
In another preferred embodiment, the polymer of formula (II) has a molecular weight of 500 to 100000g/mol.
In another preferred embodiment, the inert solvent is selected from the group consisting of: a C 1-10 alkane solvent, a C 6-12 aromatic hydrocarbon solvent, or a combination thereof; preferably, dichloromethane, chloroform, dichloroethane, trichloroethane, n-hexane, cyclohexane, chlorobenzene, toluene, xylene, trimethylbenzene, or combinations thereof.
In another preferred embodiment, the catalyst is selected from the group consisting of: chloroplatinic acid, chloroplatinic acid-isopropanol solution, methyl vinyl siloxane platinum complex, karstedt catalyst, or a combination thereof.
In another preferred embodiment, the reaction time is from 1 to 25 hours; preferably 2-20h; more preferably 3-17h.
In another preferred embodiment, the preparation method of the modified polymer specifically comprises the following steps: adding a polymer shown in a formula (II) and a silane compound containing a crosslinkable group shown in a formula (III) into an inert solvent, heating, adding a catalyst, and stirring for reaction to obtain a modified polymer shown in the formula (I).
In another preferred embodiment, the reaction further comprises a post-treatment step: after the reaction is finished, filtering, settling and drying to obtain the modified polymer shown in the formula (I).
In another preferred embodiment, the method has the following features:
(a) The molar ratio of the polymer of the formula (II) to the silane compound containing the crosslinkable group shown in the formula (III) is 1 (0.01-2); preferably 1 (0.2 to 0.8), more preferably 1 (0.3 to 0.6);
(b) The molar volume ratio of the crosslinkable group-containing silane compound represented by the formula (III) to the inert solvent is 0.05 to 0.5mol/L, preferably 0.06 to 0.3mol/L; and/or
(C) The mass molar ratio of the catalyst to the crosslinkable group-containing silane compound of the formula (III) is from 0.025 to 0.25g/mol, preferably from 0.05 to 0.2g/mol; and/or
(D) The reaction temperature is 30-160 ℃; preferably 50-150 ℃; more preferably 60-130 deg.c.
In a third aspect of the present invention, there is provided a crosslinkable group-containing silane/siloxane compound of formula (III),
Wherein R 1、R2、R3、R4 and R 5 are as described in the first aspect of the invention.
In another preferred embodiment, n 4 is 0, R 3 and R 4 are both methyl, and R 5 is
In another preferred embodiment, n 4 is 0, R 3 and R 4 are both methyl, and R 5 is
In another preferred embodiment, n 4 is 0, R 3 and R 4 are both methyl, and R 5 is
In another preferred embodiment, the crosslinkable group-containing silane compound of formula (III) is
In another preferred embodiment, the crosslinkable group-containing silane compound of formula (III) is
In another preferred embodiment, the crosslinkable group-containing silane compound of formula (III) is
In a fourth aspect of the present invention, there is provided a cured product obtained by crosslinking a cured material, wherein the cured material is the modified polymer of the first aspect of the present invention, or a blend of the modified polymer of the first aspect of the present invention with other curable monomers or polymers.
In another preferred embodiment, the crosslinking reaction is a reaction in which a crosslinkable group or bond participates.
In another preferred embodiment, the other curable monomer or polymer is a low dielectric polymer selected from the group consisting of: low dielectric polyimide, polyphenylene oxide, polytetrafluoroethylene, polyolefin, epoxy resin, cyanate ester resin, bismaleimide resin, or combinations thereof.
In another preferred embodiment, the modified polymer of the first aspect of the present invention is present in the cured material in an amount of 10% to 100%, preferably 30% to 100%, more preferably 50% to 100% by mass.
In another preferred example, the cured product is a polymer having a three-dimensional network structure obtained by a crosslinking reaction.
In another preferred embodiment, the cured product is a resin.
In another preferred embodiment, the degree of crosslinking of the cured product is 50% to 100%, preferably 70% to 100%.
In another preferred embodiment, the cured product has one or more of the following characteristics:
A dielectric constant of 2.3 to 2.7 (10 GHz), preferably 2.3 to 2.5;
(ii) a dielectric loss of 3.0X10 -4～2.0×10-3 (10 GHz), preferably 3.0 to 8.0X10 -4;
(iii) a glass transition temperature of 200 to 420 ℃, preferably 300 to 400 ℃;
(iv) the coefficient of thermal expansion is 60 to 120 ppm/. Degree.C (room temperature to 300 ℃ C.), preferably 70 to 110 ppm/. Degree.C; and/or
(V) the water absorption rate is 0.05-0.20% (after soaking in boiling water for 12-48 hours).
In a fifth aspect of the present invention, there is provided a method for producing a cured product according to the fourth aspect of the present invention, comprising the steps of:
Heating and curing the curing raw material under the protection of inert gas, so as to obtain a cured product; wherein the curing raw material is the modified polymer of the first aspect of the invention or the blend of the modified polymer of the first aspect of the invention and other heat curable monomers or polymers.
In another preferred embodiment, the inert gas is selected from the group consisting of: nitrogen and argon.
In another preferred example, the heat curing is direct heat curing, or the curing raw material is dissolved in an organic solvent to be cured, thereby obtaining a cured product.
In another preferred embodiment, the organic solvent is selected from the group consisting of: a C 1-10 alkane solvent, a C 6-12 aromatic hydrocarbon solvent, an ether solvent, an amide solvent, a sulfone solvent, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or a combination thereof.
In another preferred embodiment, the heat curing is carried out at a temperature of 100 to 350 ℃, preferably 150 to 300 ℃.
In another preferred embodiment, the heat curing is a temperature programmed curing.
In another preferred embodiment, the heat curing includes: curing for 1-6 h at 190-220 ℃, then curing for 3-6 h at 220-250 ℃, and then curing for 0.5-3 h at 250-300 ℃;
In another preferred embodiment, the heat curing includes: curing for 1-4 h at 190-220 ℃, then curing for 4-6 h at 220-250 ℃ and then curing for 1-3 h at 250-300 ℃.
In a sixth aspect of the present invention, there is provided an article prepared from or comprising the modified polymer of the first aspect of the present invention or the cured product of the fourth aspect of the present invention.
In another preferred embodiment, the article is obtained by heat curing a preform of the curing raw material.
In another preferred embodiment, the preform is formed by a forming process selected from the group consisting of: filling, solution spin coating, or solution drop coating.
In another preferred embodiment, the solution spin coating or solution drop coating includes the steps of: dissolving the curing raw material or the prepolymer of the curing raw material in a second inert solvent to prepare a solution, and then carrying out spin coating or drip coating;
Wherein the prepolymer is a polymer obtained by dissolving a curing raw material in a second inert solvent and heating and crosslinking.
In another preferred embodiment, the second inert solvent is selected from the group consisting of: a C 1-10 alkane solvent, a C 6-12 aromatic hydrocarbon solvent, an ether solvent, an amide solvent, a sulfone solvent, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or a combination thereof.
In another preferred embodiment, the article is a substrate and a film formed from the cured raw material applied to the surface of the substrate.
In another preferred embodiment, the article is selected from the group consisting of: a low dielectric film substrate material, a low dielectric film, a low dielectric constant matrix resin, a low dielectric encapsulation material, a high frequency low dielectric constant material, and a low dielectric constant photo-patterning material.
In a seventh aspect of the invention there is provided a use of an article according to the sixth aspect of the invention for the preparation of a high frequency low dielectric constant material, wherein the high frequency low dielectric constant material is selected from the group consisting of: a low dielectric film substrate material, a low dielectric film, a low dielectric constant matrix resin, a low dielectric encapsulation material, and a low dielectric constant photo-patterning material.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
FIG. 1 is a DSC curve (10deg.C/min, N 2) of polybutadiene having different benzocyclobutene side chain content
FIG. 2 is a TGA curve (5 ℃ C./min, N 2) for polybutadiene having different benzocyclobutene side chain content
FIG. 3 is a graph showing the change in water absorption after curing of polybutadiene having different benzocyclobutene side chain contents.
Detailed Description
The inventors have made extensive and intensive studies to provide a heat-curable hydrocarbon resin for the first time. The hydrocarbon resin takes 1, 2-polybutadiene as a main chain skeleton, silane with cross-linking groups is connected to side chains of the hydrocarbon resin, and the material with low dielectric constant and low dielectric loss is obtained by adjusting the content of double bonds in the side chains of the skeleton, and the hydrocarbon resin has low dielectric constant and extremely low dielectric loss at 10GHz, has high modulus, low water absorption and good heat resistance, and can be used as a low dielectric constant matrix resin or packaging material in the fields of high-frequency communication, microelectronics industry, aerospace and the like. Based on this, the inventors completed the present invention.
Terminology
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …", or "consisting of …".
As used herein, "halogen" or "halogen atom" refers to F, cl, br, and I. More preferably, the halogen or halogen atom is selected from F, cl and Br. "halogenated" means substituted with an atom selected from F, cl, br, and I.
In the present invention, "C1-C6 alkyl" means a straight-chain or branched alkyl group comprising 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, neopentyl, t-pentyl, or the like. "C1-C4 alkyl" has similar meaning.
In the present invention, the term "C2-C6 alkenyl" refers to a straight or branched alkenyl group having 2 to 6 carbon atoms containing one double bond, including without limitation ethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl and the like.
In the present invention, the term "C2-C6 alkynyl" refers to a straight or branched chain alkynyl group having 2 to 6 carbon atoms containing one triple bond, and includes, without limitation, ethynyl, propynyl, butynyl, isobutynyl, pentynyl, hexynyl and the like.
In the present invention, the term "C3-C6 cycloalkyl" refers to a cyclic alkyl group having 3 to 6 carbon atoms in the ring, including, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. "C3-C4 cycloalkyl" has similar meanings.
In the present invention, the term "C1-C6 alkoxy" refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms (C1-C6 alkyl-O-), including without limitation methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like. Preferably C1-C4 alkoxy.
In the present invention, the term "3-7 membered cycloalkoxy group" means a cyclic group having 1 oxygen atom and 2-6 ring atoms in the ring, and includes, without limitation, cyclopropyl, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and the like.
In the present invention, the term "C2-C6 alkenyloxy" refers to a straight or branched chain alkenyloxy group (C2-C6 alkenyl-O-), having 2 to 6 carbon atoms, including, without limitation, ethyleneoxy, propyleneoxy, isopropyleneoxy, butyleneoxy, and the like. Preferably C2-C4 alkenyloxy.
In the present invention, the term "C2-C6 alkynyloxy" means a straight-chain or branched alkynyloxy group (C2-C6 alkynyl-O-) having 1 to 6 carbon atoms, and includes, without limitation, ethynyloxy, propynyloxy, isopropenyloxy, butynyloxy and the like. Preferably C2-C4 alkynyloxy.
In the present invention, the term "C1-C6 alkylthio" means a straight-chain or branched alkylthio group (C1-C6 alkyl-S-) having 1 to 6 carbon atoms, and includes, without limitation, methylthio, ethylthio, propylthio, isopropylthio, butylthio and the like. C1-C4 alkylthio is preferred.
In the present invention, the term "C2-C6 alkenylthio" means a straight-chain or branched alkenylthio group (C2-C6 alkenyl-S-) having 1 to 6 carbon atoms, and includes, without limitation, vinylthio, propenylthio, isopropenylthio, butenylthio and the like. C2-C4 alkenylthio is preferred.
In the present invention, the term "C2-C6 alkynylthio" refers to a straight or branched alkynylthio group (C2-C6 alkynyl-S-) having 1 to 6 carbon atoms, including, without limitation, ethynylthio, propynylthio, isopropenynylthio, butynylthio and the like. Preferably C2-C4 acetylenic thio.
In the present invention, the term "plurality" means 1 to 7.
In the present invention, the term 1-6 means 1,2, 3, 4, 5 or 6. Other similar terms have similar meanings.
The term "ester group" has the structure-C (O) -O-R ' or R ' -C (O) -O-wherein R ' independently represents hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, heteroaryl, heterocyclyl, as defined above.
The term "ureido" refers to
The term "C1-C6 alkylamino" refers to a group having the structure-C1-C6 alkyl-NH 2 or C1-C6 alkyl-NH-with the other groups having similar definitions.
In the present application, the term "aryl" means a conjugated hydrocarbon ring system group having 6 to 10 carbon atoms as part of a group or other group. For the purposes of the present application, aryl groups may be monocyclic, or bicyclic; it may be a bridged, spiro or fused ring structure. Examples of aryl groups include, but are not limited to, phenyl, naphthyl.
In the present invention, the term "C6-C10 aryloxy" refers to a group having a C1-C6 aryl-O-structure.
As used herein, the term "5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, S and O" refers to a cyclic aromatic group having 5-10 atoms and wherein 1-3 atoms are heteroatoms selected from the following group N, S and O. It may be a single ring or may be in the form of a fused ring. Specific examples may be pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1, 2, 3) -triazolyl, and (1, 2, 4) -triazolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, and the like.
As used herein, the term "5-6 membered heterocyclyl" refers to a cyclic structure having 5-6 ring atoms, and wherein 1-3 are heteroatoms each independently selected from N, S and O.
In the present invention, the term "substituted" means that one or more hydrogen atoms on a particular group are replaced with a particular substituent. The specific substituents are those described in the foregoing for each of the examples or are those found in each of the examples. Unless otherwise specified, a substituted group may have a substituent selected from a specific group at any substitutable site of the group, which may be the same or different at each position. Those skilled in the art will appreciate that combinations of substituents contemplated by the present invention are those that are stable or chemically achievable. Such as (but not limited to): deuterium, halogen, hydroxy, cyano, amino, alkylamino, carbonyl, C1-6 alkyl, C1-6 alkoxy, C3-6 cycloalkyl, halogenated C1-6 alkyl, halogenated C1-6 alkoxy, halogenated C3-6 cycloalkyl, haloalkylamino, 3-7 membered heterocyclyl, aryl, heteroaryl, C2-6 acyl, C2-6 ester, C2-6 alkynyl, C2-6 alkenyl, and the like.
The compounds of the present application may be prepared by a variety of synthetic methods well known to those skilled in the art, including the specific embodiments listed below, embodiments formed by combining the specific embodiments with other chemical synthetic methods, and equivalent alternatives well known to those skilled in the art, preferred embodiments including but not limited to the examples of the present application.
As used herein, the term "crosslinkable curing group" refers to a group or bond that can undergo a crosslinking reaction, and/or a group having unsaturation.
As used herein, the "silane compound" includes "siloxane compound".
Crosslinkable group-containing silanes/siloxanes of the formula (III)
The crosslinkable group-containing silanes/siloxanes used in the present invention may be those known in the art or may be commercially available and may be prepared by conventional synthetic methods in the art.
Specifically, the invention also provides a method for preparing silane/siloxane containing crosslinkable groups, which is shown in a formula (III), and the preparation method comprises the following steps:
Method (1-1): reacting hydrogen-containing chlorosilane or hydrogen-containing siloxane B with halogenated benzocyclobutene, halogenated vinylbenzocyclobutenyl or halogenated phenyl trifluorovinyl ether A under the protection of inert gas to obtain silane containing benzocyclobutene, vinylbenzocyclobutenyl or trifluorovinyl ether, namely a compound of a formula (III), wherein n 4 = 0, X is halogen, and R is C1-6 alkyl;
Method (2-1): reacting with halogenated benzocyclobutene, halogenated vinylbenzocyclobutenyl or halogenated phenyl trifluorovinyl ether A and Mg under the protection of inert gas to obtain a Grignard reagent C, and reacting with hydrogen-containing chlorosilane or hydrogen-containing siloxane B to obtain silane containing benzocyclobutene, vinylbenzocyclobutenyl or phenyl trifluorovinyl ether, namely a compound shown in a formula (III), wherein X is halogen, R is C1-6 alkyl, and n 4 = 0;
Method (1-2): under the protection of inert gas, siloxane D containing benzocyclobutene, halogenated vinyl benzocyclobutenyl or phenyl trifluoro vinyl ether is reacted with disilane hydrogen E to obtain silane containing benzocyclobutene, vinyl benzocyclobutenyl or phenyl trifluoro vinyl ether, namely a compound of a formula (III), wherein R is C1-6 alkyl, n 4 is equal to 0, and n4 is a positive integer of 1-12.
Method (2-2): under the protection of inert gas, siloxane D containing benzocyclobutene, vinylbenzocyclobutenyl or phenyl trifluoro vinyl ether is reacted with disilane hydrogen E to obtain silane containing benzocyclobutene, vinylbenzocyclobutenyl or phenyl trifluoro vinyl ether, namely a compound of a formula (III), wherein R is C1-6 alkyl, n 4 is equal to 0, and n4 is a positive integer of 1-12.
The thermally curable low dielectric constant polymers of the invention
The invention provides a heat-curable low dielectric constant polymer, wherein a monomer of the low dielectric constant polymer has a structure shown in the following formula I:
wherein, the definition of each group and each symbol are as described in the specification.
The heat-curable polybutadiene of the present invention exhibits high heat resistance (T5 d >420 ℃) after curing, low water absorption (as low as 0.05%), high glass transition temperature (Tg >400 ℃), low coefficient of thermal expansion (room temperature-300 ℃ C., CTE as low as 72 ppm/. Degree.C.), and good dielectric properties (dielectric constant as low as 2.32, dielectric loss as low as 3.4X10 -4) at high frequencies of 10 GHz.
The polymers of the present invention may also be used as modifiers in other materials where desired to improve the dielectric properties of the material.
The heat curable polymers of the present invention can be prepared using synthetic methods conventional in the art. Specifically, the polymer of the invention is formed by crosslinking a polymer shown in a formula (II) and a silane compound/siloxane compound containing a crosslinkable group shown in a formula (III) under the action of a catalyst.
Wherein, the definition of each group and symbol is as described in the specification.
Preferably, the catalyst is selected from the group consisting of: chloroplatinic acid, chloroplatinic acid-isopropanol solution, methyl vinyl siloxane platinum complex, karstedt catalyst, or combinations thereof
The molecular weight of the polymer of the formula (II) is 500-100000 mW.
The silane compound/siloxane compound containing a crosslinkable group represented by the formula (III) contains at least one crosslinkable group. Wherein the crosslinkable group refers to a group or a chemical bond that can undergo a crosslinking reaction (e.g., thermal crosslinking), and includes, but is not limited to, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), carbamate (-O-C (O) -NH-), ureido (-NH-C (O) -NH-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-C (O) O-), alkenyl, alkynyl, phenyl, heterocyclyl, cycloalkenyl, cycloalkynyl; and/or the compound shown in the formula III has 1-10 unsaturations; preferably 2-6 unsaturations.
Cured product
The invention also provides a cured product, which is a polymer with a three-dimensional network structure obtained by a crosslinking reaction. It is obtained by the cross-linking reaction of the solidifying raw material. In general, the curing materials are polymers of the first aspect of the invention, and may include other thermally curable monomers or polymers known in the art.
Preferably, other thermally curable monomers or polymers known in the art include low dielectric polyimides, polyphenylene oxides, polytetrafluoroethylene, or combinations thereof.
Preferably, other thermally curable monomers or polymers known in the art are low dielectric polymers.
Preferably, the mass fraction of the polymer in the curing material is 10% to 100%, preferably 30% to 100%, more preferably 50% to 100%.
Preferably, the cured product is a resin.
Preferably, the degree of crosslinking of the cured product is 50% to 100%, preferably 70% to 100%.
The cured product of the present invention is insoluble and has excellent low dielectric properties, excellent thermo-mechanical properties, low water absorption and excellent surface smoothness, especially high frequency low dielectric properties
Specifically, the cured product has one or more of the following characteristics:
A dielectric constant of 2.3 to 2.7 (10 GHz), preferably 2.3 to 2.5;
(ii) a dielectric loss of 3.0X10-4 to 2.0X10-3 (10 GHz), preferably 3.0 to 8.0X10-4;
(iii) a glass transition temperature of 200 to 420 ℃, preferably 300 to 400 ℃;
(iv) the coefficient of thermal expansion is 60 to 120 ppm/. Degree.C (room temperature to 300 ℃ C.), preferably 70 to 110 ppm/. Degree.C;
(v) the water absorption rate is 0.05-0.20% (after soaking in boiling water for 12-48 hours).
In addition, the invention also provides a preparation method of the cured product, which specifically comprises the following steps:
Heating and curing the curing raw material under the protection of inert gas, so as to obtain a cured product; wherein the curing raw material is the polymer of the first aspect of the invention or the blend of the polymer of the first aspect of the invention and other heat curable monomers or polymers.
Wherein the inert gas is an inert gas commonly used in the art, preferably nitrogen, argon, or a combination thereof.
Specifically, "heat curing" in the present invention includes direct heat curing of a curing raw material and curing by dissolving the curing raw material in an organic solvent, thereby obtaining a cured product.
Preferably, the organic solvent is selected from the group consisting of: a C1-10 alkane solvent, a C6-12 aromatic hydrocarbon solvent, an ether solvent, an amide solvent, a sulfone solvent, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or a combination thereof.
Preferably, the heating and curing is temperature programming and curing; the curing temperature is 100 to 350 ℃, preferably 150 to 300 ℃.
Preferably, the heat curing comprises: curing for 1-6 h at 190-220 ℃, then curing for 3-6 h at 220-250 ℃, and then curing for 0.5-3 h at 250-300 ℃;
More preferably, the heat curing comprises: curing for 1-4 h at 190-220 ℃, then curing for 4-6 h at 220-250 ℃ and then curing for 1-3 h at 250-300 ℃.
Use of the same
The invention also provides a polymer according to the first aspect of the invention and the use of the cured product according to the third aspect of the invention for preparing a high frequency low dielectric constant material, wherein the high frequency low dielectric constant material is selected from the group consisting of: a low dielectric film substrate material, a low dielectric film, a low dielectric constant matrix resin, a low dielectric encapsulation material, and a low dielectric constant photo-patterning material.
Specifically, the cured raw material of the present invention can be obtained by preforming and then heat-curing.
The preforming means that the polymer is used as a coating layer to coat or pour the surface with the requirement into the required shape by means of pouring, spin coating or dripping. The solidifying raw material can be directly preformed, or can be dissolved in a second inert solvent to prepare a prepolymer, and the prepolymer is used for preforming.
Preferably, the second inert solvent is selected from the group consisting of: a C1-10 alkane solvent, a C6-12 aromatic hydrocarbon solvent, an ether solvent, an amide solvent, a sulfone solvent, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or a combination thereof.
Compared with the prior art, the invention has the main advantages that:
(1) The invention provides a thermosetting polymer with a structure shown in a formula I, which has excellent film forming performance and low thermal crosslinking temperature.
(2) According to the invention, through simple hydrosilylation reaction of 1, 2-polybutadiene, thermosetting polymers with different thermosetting side group contents and structures shown in formula I are obtained, the preparation method is simple, the reaction conditions are mild, and the method is suitable for large-scale industrial production.
(3) The thermosetting polymer of the invention exhibits high heat resistance (T5 d >420 ℃) after curing, low water absorption (as low as 0.05%), high glass transition temperature (Tg >400 ℃), low coefficient of thermal expansion (room temperature-300 ℃ C., CTE as low as 72 ppm/. Degree.C.), and good dielectric properties (dielectric constant as low as 2.32, dielectric loss as low as 3.4X10 -4) at high frequencies of 10 GHz.
(4) The thermosetting polymer can be directly and thermally cured to prepare a sheet, and can be blended with a filler to obtain a low dielectric constant material with excellent performance.
(5) The thermosetting polymer is a novel thermosetting hydrocarbon resin, and can be used as a high-performance matrix resin or packaging material in the fields of high-frequency communication, large-scale integrated circuits, microelectronics industry, aerospace and the like.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, which do not address specific conditions in the following examples, are generally in accordance with the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are presented for illustrative purposes only.
Example 1: benzocyclobutene silahydrogen
150.0Mmol of magnesium turnings, 150mL of tetrahydrofuran, 150.0mmol of dimethylchlorosilane and one small particle of I 2 (about 30 mg) are added into a 250mL dry three-neck flask under the protection of nitrogen gas, then 100.0mmol of 4-bromobenzocyclobutene is slowly added dropwise, heating is carried out for initiation, the solution is kept slightly boiling, and the solution is reacted overnight at room temperature after the dropwise addition is finished. After the completion of the reaction, n-hexane was added, the salt was removed by filtration, and the solvent was concentrated and distilled under reduced pressure (external temperature 80 ℃ C., internal temperature 61 ℃ C.) to give 14.08g of a colorless transparent liquid compound S1 in total in the yield of 87％.1H NMR(500MHz,Chloroform-d),δ(ppm):7.48(d,J＝7.1Hz,1H),7.33(s,1H),7.15(d,J＝7.1Hz,1H),4.50(m,1H),3.27(s,4H),0.41(d,J＝3.9Hz,6H).13C NMR(150MHz,Chloroform-d),δ(ppm):147.44,145.58,135.58,132.42,127.85,122.16,30.03,29.92,-3.33(2C).
Example 2: vinylbenzocyclobutenyl silahydrogen
200ML of acetonitrile, 639.7mmol of 4-bromobenzocyclobutene, 767.7mmol of vinyldimethylethoxysilane, 31.9mmol of palladium acetate, 127.9mmol of tris- (2-methylphenyl) phosphine and 1407.4mmol of triethylamine are added to a 1000mL dry three-necked flask under the protection of nitrogen gas, nitrogen gas is bubbled for 3 hours, and the temperature is raised to 105 ℃ and the mixture is refluxed overnight. After the reaction is finished, the solvent is dried by rotation after filtration, and the solvent is directly thrown into the next reaction step. Another 500mL dry three-necked flask was taken, 50mL dry THF was added, 100.0mmol S2 was added, and the flask was placed under ice bath, 100.0mmol LiAlH 4 was added, and the temperature was slowly raised to room temperature, and the reaction was continued for 5 hours. After the reaction is finished, adding a small amount of water for quenching under ice bath, extracting with petroleum ether, drying with anhydrous sodium sulfate, filtering, spin-drying the solvent, and then distilling under reduced pressure to obtain a total of 12.2g of colorless transparent liquid compound S3, wherein the yield is 65％.1H NMR(600MHz,CDCl3)δ＝7.25(d,J＝7.6,1H),7.16(s,1H),6.88(d,J＝18.8,1H),6.38(d,J＝18.8,1H),4.23(1H,m)3.16(s,4H),0.15(s,9H);13C NMR(101MHz,CDCl3)δ＝146.1,146.0,144.3,137.4,127.6,126.0,122.6,120.0,29.6,29.4,-1.0.
Example 3: synthesis of polybutadiene PB-g-B 5 containing 5% benzocyclobutene side chain
40.0Mmol of Polymer II (m: n=9:1), 10mL of mesitylene, 2.4mmol of Compound S1 were added to a 100mL two-necked flask under nitrogen protection, the temperature was slowly raised to 120℃and 0.1mL of H 2PtCl6 solution (10 mg/mL of isopropanol solution) was added, and the reaction was continued at 120℃for 3 hours. Removing solvent under reduced pressure after stopping reaction, adding neutral alumina into a funnel, filtering to remove catalyst, and settling in methanol for 3 times to obtain colorless polymer PB-g-B 5 total 2.19g, yield ：80％.1H NMR(400MHz,Chloroform-d)δ7.34(d,J＝7.0Hz,1H),7.19(s,1H),7.05(d,J＝7.0Hz,1H),5.57–5.32(m,21H),5.08–4.66(m,30H),3.18(s,4H),2.12–1.89(m,26H),1.64–4.55(m,4H),1.25–1.16(m,39H),0.80–0.63(m,4H),0.22(s,6H).13C NMR(151MHz,Chloroform-d)δ146.95,145.61,144.40–141.99(m),137.80,131.95,127.46,122.00,115.21–113.90(m),39.09–38.83(m),30.06,29.91,18.10,13.14,1.17,0.15,-2.68.29Si NMR(119MHz,Chloroform-d)δ-1.90.
Example 4: synthesis of polybutadiene PB-g-B 30 containing 30% benzocyclobutene side chain
To a 100mL two-necked flask under nitrogen protection was added 30.0mmol of Polymer II (m: n=9:1), 30mL of mesitylene, 10.0mmol of Compound S1, slowly warmed to 120℃and 0.1mL of H 2PtCl6 solution (10 mg/mL of isopropanol solution) and reacted at 120℃for 3 hours. Removing solvent under reduced pressure after stopping reaction, adding neutral alumina into a funnel, filtering to remove catalyst, and settling in methanol for 3 times to obtain colorless polymer PB-g-B 30 total 2.56g, yield ：83％.1H NMR(400MHz,Chloroform-d)δ7.34(d,J＝6.5Hz,1H),7.19(s,1H),7.04(d,J＝5.9Hz,1H),5.65–5.19(m,4H),5.12–4.63(m,5H),3.18(s,4H),2.11–1.89(m,5H),1.63–1.59(m,1H),1.26–1.17(m,11H),0.80–0.63(m,2H),0.22(s,6H).13C NMR(151MHz,Chloroform-d)δ146.95,145.61,144.40–141.99(m),137.80,131.95,127.46,122.00,115.21–113.90(m),39.09–38.83(m),30.06,29.91,18.10,13.14,1.17,0.15,-2.68.29Si NMR(119MHz,Chloroform-d)δ-1.94.
Example 5: synthesis of polybutadiene PB-g-B 60 containing 60% benzocyclobutene side chain
To a 50mL two-necked flask under nitrogen protection was added 20.0mmol of Polymer II (m: n=9:1), 20mL of mesitylene, 13.0mmol of Compound S1, slowly warmed to 120℃and 0.1mL of H 2PtCl6 solution (10 mg/mL of isopropanol solution) and reacted at 120℃for 9 hours. Removing solvent under reduced pressure after stopping reaction, adding neutral alumina into a funnel, filtering to remove catalyst, and settling in methanol for 3 times to obtain colorless polymer PB-g-B 60 total 2.84g, yield ：90％.1H NMR(400MHz,Chloroform-d)δ7.32(s,1H),7.18(s,1H),7.02(s,1H),5.35–5.31(m,1H),4.89–4.81(m,1H),3.16(s,4H),2.04–1.88(m,2H),1.26–1.13(m,7H),0.63–0.53(m,2H),0.21(s,6H).13C NMR(151MHz,Chloroform-d)δ146.92,145.59,144.19–143.45(m),137.79,131.95,127.45,122.01,114.79–144.03(m),39.52(d,J＝124.2Hz),39.93–33.17(m),30.06,29.90,27.63–26.38(m),11.42(br),-2.67.29Si NMR(119MHz,Chloroform-d)δ-2.02.
Example 6: synthesis of polybutadiene PB-g-B 100 containing 100% benzocyclobutene side chain
To a 100mL two-necked flask under nitrogen protection was added 20.0mmol of Polymer II (m: n=9:1), 30mL of mesitylene, 16.0mmol of Compound S1, slowly warmed to 120℃and 0.1mL of H 2PtCl6 solution (10 mg/mL of isopropanol solution) and reacted at 120℃for 19 hours. Removing solvent under reduced pressure after stopping reaction, adding neutral alumina into a funnel, filtering to remove catalyst, and settling in methanol for 3 times to obtain colorless polymer PB-g-B 100 total 4.0g, yield ：89％.1H NMR(400MHz,Chloroform-d)δ7.31(s,3H),7.17(s,3H),7.00(s,3H),5.29(s,1H),3.14(s,12H),1.92(br,2H),1.27(br,18H),0.62(br,7H),0.20(s,12H).13C NMR(151MHz,Chloroform-d)δ146.76,145.43,137.61,131.81,127.30,121.88,38.39(br),33.80(br),29.92,29.76,26.93(br),11.22(br),-2.78.29Si NMR(119MHz,Chloroform-d)δ-2.07.
Example 7: property study of cured and corresponding cured products of thermoset polybutadiene PB-g-B 5
The target polymer PB-g-B 5 prepared in example 2 was taken and placed in a tube furnace, bubbles were removed at 150℃and cured for 3 hours at 210℃and for 3 hours at 240℃and for 2 hours at 270℃to give cured resin cured-PB-g-B 5.
The cured sample was ground to a uniform wafer and tested for dielectric properties, which indicated a dielectric constant of 2.32 at 10GHz and a dielectric loss of 7.3x10 -4. The TGA test results showed that the cured resin had a 5% thermal weight loss temperature (T 5d) of 427 ℃. The DMA test results showed that the glass transition temperature of the cured resin was 181 ℃. CTE tests show that the coefficient of thermal expansion is 117ppm/°c over the range of room temperature to 200 ℃. As shown in FIG. 3, after the cut-PB-g-B 5 was immersed in boiling water for 48 hours, the water absorption was measured to be 0.18%.
EXAMPLE 8 Property study of the cured and corresponding cured products of thermosetting polybutadiene PB-g-B 30
The target polymer PB-g-B 30 prepared in example 3 was taken and placed in a tube furnace, bubbles were removed at 150℃and cured for 3 hours at 210℃and for 3 hours at 240℃and for 2 hours at 270℃to give cured resin cured-PB-g-B 30.
The cured sample was ground to a uniform wafer and tested for dielectric properties, which indicated a dielectric constant of 2.34 and a dielectric loss of 3.6X10 -4 at 10 GHz. The TGA test results showed that the cured resin had a 5% thermal weight loss temperature (T 5d) of 437 ℃. The DMA test result showed that the glass transition temperature of the cured resin was 209 ℃. CTE tests show that the coefficient of thermal expansion is 88ppm/°c over the range of room temperature to 200 ℃. As shown in FIG. 3, after the cut-PB-g-B 30 was immersed in boiling water for 48 hours, the water absorption was measured to be 0.05%.
EXAMPLE 9 Property study of the cured and corresponding cured products of thermosetting polybutadiene PB-g-B 60
The target polymer PB-g-B 60 prepared in example 4 was taken and placed in a tube furnace, bubbles were removed at 150℃and cured for 3 hours at 210℃and for 3 hours at 240℃and for 2 hours at 270℃to give cured resin cured-PB-g-B 60.
The cured sample was ground to a uniform wafer and tested for dielectric properties, which indicated a dielectric constant of 2.37 at 10GHz and a dielectric loss of 8.3x10 -4. The TGA test results showed that the cured resin had a 5% thermal weight loss temperature (T 5d) of 446 ℃. The DMA test results show that the glass transition temperature of the cured resin is greater than 400 ℃. CTE tests show that the coefficient of thermal expansion is 72ppm/°c over the range of room temperature to 300 ℃. As shown in FIG. 3, after the cut-PB-g-B 60 was immersed in boiling water for 48 hours, the water absorption was measured to be 0.08%.
Example 10: property study of cured and corresponding cured products of thermoset polybutadiene PB-g-B 100
The target polymer PB-g-B 100 prepared in example 5 was taken and placed in a tube furnace, bubbles were removed at 150℃and cured for 3 hours at 210℃and for 3 hours at 240℃and for 2 hours at 270℃to give cured resin cured-PB-g-B 100.
The cured sample was ground to a uniform wafer and tested for dielectric properties, which indicated a dielectric constant of 2.41 and a dielectric loss of 1.10X10 -3 at 10 GHz. The TGA test results showed that the 5% thermal weight loss temperature (T 5d) of the cured resin was 453 ℃. The DMA test results show that the glass transition temperature of the cured resin is greater than 400 ℃. CTE tests show that the coefficient of thermal expansion is 81ppm/°c over the range of room temperature to 300 ℃. As shown in FIG. 3, after the cut-PB-g-B 100 was immersed in boiling water for 48 hours, the water absorption was measured to be 0.17%.
Discussion of the invention
The dielectric constants of the low dielectric substrate materials commonly used at present are not too large (2.0-3.5), but the dielectric losses are different in magnitude (10 -2～10-4), so that the dielectric losses of the low dielectric materials have more important influence on high-frequency and high-speed circuits.
The most commonly used low dielectric substrate materials in the high-frequency and high-speed circuit at present mainly comprise Polytetrafluoroethylene (PTFE), thermosetting polyphenylene oxide (PPO) and hydrocarbon resin, wherein PTFE is most widely applied in the high-frequency and high-speed circuit because of extremely low dielectric constant (2.2-2.6), dielectric loss (less than or equal to 2 multiplied by 10 -3) and excellent thermal stability and flame retardance, but PTFE also has obvious short plates. PTFE as a thermoplastic polymer has relatively poor mechanical strength and a high fluorine content greatly reduces the adhesion between the material and the conductor, is difficult to process and is expensive. Thermosetting PPO has more outstanding adhesion and mechanical properties than PTFE and is more advantageous in terms of processability, but it is difficult to meet higher requirements with respect to dielectric constants (2.6 to 3.3) and dielectric losses (3×10 -3～7×10-3). Hydrocarbon resin is used as resin with ultralow polarity, the dielectric constant (2.2-2.5) and dielectric loss (2.5 multiplied by 10 -3～3.5×10-3) of the hydrocarbon resin are closer to those of PTFE, the price is lower, but the thermal stability is poorer, and the curing temperature is higher.
The invention starts from the molecular structure of 1, 2-polybutadiene, and adopts hydrosilylation reaction to introduce a heat-curable group on vinyl of a side chain of the polybutadiene, thereby obtaining a thermosetting polymer. The polymer provided by the invention shows high heat resistance (T5 d >420 ℃), low water absorption (as low as 0.05%), high glass transition temperature (Tg >400 ℃), low thermal expansion coefficient (room temperature-300 ℃ and CTE as low as 72 ppm/DEGC), and good dielectric properties (dielectric constant as low as 2.32 and dielectric loss as low as 3.4X10 -4) under the high-frequency condition of 10GHz after being cured.
By adjusting the addition rate of vinyl groups, the dielectric properties and mechanical properties of the material can be adjusted. In general, the higher the addition rate, the better the mechanical properties and thermal stability after curing, while the dielectric constant rises slightly. It is worth mentioning that when the content of the introduced heat-curable groups is too low, the double bonds of the polybutadiene side chains cannot be completely crosslinked, and the dielectric loss of the polymer increases significantly. When the content of the introduced benzocyclobutene group is 30% of the double bonds of the side chain, the lowest dielectric loss of 3.6X10 -4 is obtained, which is far superior to the currently known low dielectric materials applied to high-frequency and high-speed circuits.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.

Claims (10)

1. A curable modified polymer, wherein the modified polymer has a monomer structure represented by formula I:
wherein,
N 1、n2 satisfies n 1：(n1+n2) = (0.01 to 1): 1;
n 1、n2、n3 satisfies n 1:(n1+n2+n3) = (0.01 to 1): 1, a step of;
n 4 is an integer from 0 to 12;
Each R 1 and R 2 is independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido (-N=O-) cyanate (-N=O-;
R 3、R4 and R 5 are each independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy a 5-10 membered heteroaryl group having 1 to 3 heteroatoms each independently selected from N, O and S, a benzo 5-6 membered heterocyclyl group, a benzo C3-6 cycloalkyl group, a benzo C4-6 cycloalkenyl group, a benzo C4-6 cycloalkynyl group, a C1-C6 hydroxyalkyl group, a C2-C6 hydroxyalkenyl group, a C2-C6 hydroxyalkynyl group, a hydroxyphenyl group (-Ph-OH), a ureido group, an amino ester group, -CO-NH- (C1-C4 alkyl) an isocyanate group (-n=c=o), a cyanate group (-O-CN);
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), phenyl ether (Ph-O-), phenyl sulfide (Ph-S-), C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, isocyanate group, cyanate group;
wherein the monomer structure shown in the formula I contains m unsaturated degrees, and m is 2-10;
or in the monomer structure shown in the formula I Comprising p crosslinkable groups or linkages, p being from 1 to 10, wherein said crosslinkable groups or linkages are selected from the group consisting of: cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), carbamate (-O-C (O) -NH-), ureido (-NH-C (O) -NH-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-C (O) O-), alkenyl, alkynyl, phenyl, heterocyclyl, cycloalkenyl, cycloalkynyl, isocyanate, cyanate.
2. The modified polymer of claim 1, wherein n4 is 0,
R 3、R4 are each independently selected from the group consisting of: H. C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 hydroxyalkyl, phenyl, halogenated C1-C6 alkyl-substituted phenyl;
R 5 is a group containing a crosslinkable group or bond selected from the group; H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkynyl, C2-C6 hydroxyphenyl, ureido, C1- (C4-NH) isocyanate, isocyanate;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), phenyl ether (Ph-O-), phenyl sulfide (Ph-S-), C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl;
Preferably, R 5 is a group selected from the group consisting of a crosslinkable group or a bond; H. a substituted or unsubstituted group selected from the group consisting of: C2-C6 alkenyl, C2-C6 alkynyl, C6 aryl, C1-C6 alkoxy, C6 aryloxy, 5-6 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzoC 3-6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, hydroxyphenyl;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano, hydroxy, mercapto, amino, carboxyl, phenyl ether, phenyl sulfide, C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, -CO-NH- (C1-C4 alkyl);
Preferably, R 5 is a group selected from the group consisting of: vinyl, styryl, ethynyl, phenylethynyl, benzocyclobutenyl, vinylbenzocyclobutenyl, trifluorovinylphenyl ether, cyano, epoxy, cyanate, isocyanate groups.
3. The modified polymer of claim 1, wherein the modified polymer has a monomer structure selected from the group consisting of:
4. A method of preparing the modified polymer of claim 1, comprising the steps of:
reacting a polymer shown in the following formula (II) with a silane compound/siloxane compound containing a crosslinkable group shown in the formula (III) in an inert solvent under the action of a catalyst to obtain a modified polymer shown in the formula (I);
wherein,
N 0 is 1 to 2000, and n 0 and n 3 satisfy n 0：(n0+n3) = (0.01 to 1): 1, a step of;
n 4 is an integer from 0 to 12;
Each R 1 and R 2 is independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido (-N=O-) cyanate (-N=O-;
R 3、R4 and R 5 are each independently selected from the group consisting of: H. a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-C7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-to 10-membered heteroaryl having 1 to 3 heteroatoms each independently selected from N, O and S, benzo 5-to 6-membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkynyl, C2-C6 hydroxyphenyl (-hydroxy-phenyl), ureido, C4-alkyl-CO- (C4-OH), isocyanate;
By substituted is meant that one or more hydrogens on the group are replaced with a substituent selected from the group consisting of: halogen, silicon-based (-SiR 3), cyano, hydroxy, mercapto, amino, carboxyl, phenyl ether, phenyl sulfide, C1-C4 ester, C1-C4 alkyl, halogenated C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, 3-7 membered cycloalkoxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzoC 3-C6 cycloalkyl, benzoC 4-6 cycloalkenyl, benzoC 4-6 cycloalkynyl, -CO-NH- (C1-C4 alkyl); and a phenyl group having 1 to 3 substituents selected from the group consisting of: halogen, cyano, hydroxy, mercapto, amino, carboxyl, C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, isocyanate group, cyanate group;
wherein the monomer structure shown in the formula I contains m unsaturated degrees, and m is 2-10;
or in the monomer structure shown in the formula I Comprising p crosslinkable groups or linkages, p being from 1 to 10, wherein said crosslinkable groups or linkages are selected from the group consisting of: cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH 2), carboxyl (-COOH), carbamate (-O-C (O) -NH-), ureido (-NH-C (O) -NH-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-C (O) O-), alkenyl, alkynyl, phenyl, heterocyclyl, cycloalkenyl, cycloalkynyl, isocyanate, cyanate.
5. The method of claim 4, wherein the method has the following characteristics:
(a) The molar ratio of the polymer of the formula (II) to the silane compound containing the crosslinkable group shown in the formula (III) is 1 (0.01-2); preferably 1 (0.2 to 0.8), more preferably 1 (0.3 to 0.6);
(b) The molar volume ratio of the crosslinkable group-containing silane compound represented by the formula (III) to the inert solvent is 0.05 to 0.5mol/L, preferably 0.06 to 0.3mol/L; and/or
(C) The mass molar ratio of the catalyst to the crosslinkable group-containing silane compound of the formula (III) is from 0.025 to 0.25g/mol, preferably from 0.05 to 0.2g/mol; and/or
(D) The reaction temperature is 30-160 ℃; preferably 50-150 ℃; more preferably 60-130 deg.c.
6. A crosslinkable silane compound/siloxane compound of the formula (III),
Wherein R 1、R2、R3、R4 and R 5 are as described in claim 1.
7. A cured product obtained by crosslinking a curing material, wherein the curing material is the modified polymer of claim 1 or a blend of the modified polymer of claim 1 with other curable monomers or polymers.
8. A method for producing the cured product of claim 7, comprising the steps of:
Heating and curing the curing raw material under the protection of inert gas, so as to obtain a cured product; wherein the curing raw material is the modified polymer of claim 1 or the blend of the modified polymer of claim 1 and other heat curable monomers or polymers.
9. An article prepared from the modified polymer of claim 1 or the cured product of claim 7, or comprising the modified polymer of claim 1 or the cured product of claim 7.
10. Use of the article of claim 9 for the preparation of a high frequency low dielectric constant material, wherein the high frequency low dielectric constant material is selected from the group consisting of: a low dielectric film substrate material, a low dielectric film, a low dielectric constant matrix resin, a low dielectric encapsulation material, and a low dielectric constant photo-patterning material.
CN202410076271.9A 2024-01-18 2024-01-18 Thermally crosslinkable polymer with high frequency and low dielectric constant, and preparation method and application thereof Pending CN117903342A (en)

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