Thermally crosslinkable polymer having high frequency and low dielectric constant, preparation method therefor and use thereof

Abstract

A thermally curable modified polymer having high frequency and low dielectric constant, a synthesis method therefor and a use thereof. The thermally curable modified polymer has a monomer structure as shown in the following formula I. The thermally curable modified polymer can be widely applied to the fields of high-frequency communications, microelectronics industry, aerospace and the like as a low-dielectric-constant matrix resin or packaging material.

Description

A type of thermally cross-linkable polymer with high frequency and low dielectric constant and its preparation method and application Technical Field

[0001] The present invention relates to the field of thermosetting polyolefin materials, and in particular to a heat-crosslinkable polymer and a preparation method thereof, as well as application of the heat-crosslinked polymer as a high-frequency low dielectric constant material. Background Art

[0002] With the rapid development of the Internet of Things (IoT) and high-frequency communications (5G), the transmission speed and quality of electronic signals need to meet higher requirements. Compared with the fourth-generation mobile communications (4G), 5G has the characteristics of high signal transmission speed (about 10Gbps), small signal delay (<1ms) and multi-terminal access. In order to achieve high-speed and large-capacity signal transmission, 5G communication technology mainly uses sub-6GHz and millimeter wave frequency bands for signal transmission. The high transmission frequency will cause the circuit to produce obvious skin effect and ionization loss, causing the substrate to heat up and increase signal loss and energy dissipation, thereby affecting the signal transmission quality. The signal transmission loss in digital circuits mainly includes conductor loss (T LC ) and dielectric loss (T LD ), and the dielectric loss T LD The dielectric constant (D k ) and dielectric loss (D f ) has the following relationship: K represents the coefficient; f represents the frequency; c represents the speed of light. The dielectric constants of the currently commonly used low-dielectric substrate materials do not differ much (2.0 to 3.5), but the dielectric loss has an order of magnitude difference (10 -2 ~10 -4 ), so the dielectric loss of low dielectric materials has a more important impact on high-frequency and high-speed circuits.

[0003] In summary, there is an urgent need to develop a class of devices that meet the requirements of ultra-low dielectric loss (<10 -4 ), and a low dielectric material with excellent mechanical properties and processing properties. Summary of the Invention

[0004] An object of the present invention is to provide a low dielectric material having low dielectric constant and ultra-low dielectric loss as well as excellent mechanical properties and processing properties, and a preparation method thereof.

[0005] Another object of the present invention is to provide a thermosetting product having low dielectric constant and ultra-low dielectric loss and use thereof.

[0006] In a first aspect of the present invention, a curable modified polymer is provided, wherein the modified polymer has a monomer structure shown in the following formula I:

[0007] in,

[0008] n1 and n2 satisfy n1: (n1 + n2) = (0.01 to 1): 1;

[0009] n1, n2, and n3 satisfy n1:(n1+n2+n3)=(0.01-1):1;

[0010] n4 is an integer from 0 to 12;

[0011] Each R1 and R2 is independently selected from the following group: H, a substituted or unsubstituted group selected from the following group: 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 cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C 2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, urea, aminoester, isocyanate (-N=C=O), cyanate (-O-CN);

[0012] R3, R4 and R5 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, 3-7 membered cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6- C10 aryl, C6-C10 aryloxy, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl (-Ph-OH), urea, aminoester, -CO-NH-(C1-C4 alkyl), isocyanate (-N=C=O), cyanate (-O-CN);

[0013] The substitution refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of halogen, silicon (-SiR3), cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), 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, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, -CO-NH-(C1-C4 alkyl); and phenyl having 1-3 substituents selected from the group consisting of halogen, cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl, isocyanate, cyanate;

[0014] Wherein, the monomer structure represented by the formula I contains m unsaturations, and m is 2-10;

[0015] Alternatively, in the monomer structure shown in Formula I wherein p cross-linkable groups or bonds are contained, and p is 1-10, wherein the cross-linkable groups or bonds are selected from the following group: cyano group (CN), hydroxyl group (-OH), thiol group (-SH), amino group (-NH2), carboxyl group (-COOH), carbamate group (-OC(O)-NH-), urea group (-NH-C(O)-NH-), ether bond (-O-), thioether bond (-S-), ester bond (-C(O)O-), alkenyl group, alkynyl group, phenyl group, heterocyclic group, cycloalkenyl group, cycloalkynyl group, isocyanate group, and cyanate group.

[0016] In another preferred embodiment, the alkyl, alkenyl and alkynyl groups are straight-chain or branched.

[0017] In another preferred embodiment, n4 is an integer of 0-5; preferably 0-2.

[0018] In another preferred embodiment, the halogen is fluorine.

[0019] In another preferred embodiment, R1 and R2 are the same or different, preferably the same.

[0020] In another preferred embodiment, R3 and R4 are the same or different, preferably the same.

[0021] In another preferred embodiment, n2=0.

[0022] In another preferred embodiment, n3=0.

[0023] In another preferred embodiment, the curable material is heat curable.

[0024] In another preferred embodiment, n4 is 0,

[0025] R3 and 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 phenyl, and phenyl substituted with halogenated C1-C6 alkyl;

[0026] R5 is a group selected from the following group containing a crosslinkable group or bond; H, a substituted or unsubstituted group selected from the following group: 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 cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, urea, aminoester, -CO-NH-(C1-C4 alkyl), isocyanate, cyanate;

[0027] The substitution refers to the substitution of one or more hydrogen atoms on the group by a substituent selected from the group consisting of halogen, silicon (-SiR3), cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), 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 cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, unsubstituted phenyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, -CO-NH-(C1-C4 alkyl); and phenyl having 1-3 substituents selected from the group consisting of halogen, cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, C2-C4 alkynyl, halogenated C2-C4 alkynyl;

[0028] Preferably, R5 is a group selected from the group consisting of: 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, a 5-6 membered heteroaryl having 1-3 heteroatoms independently selected from N, O and S, a benzo 5-6 membered heterocyclic group, a benzo C3-6 cycloalkyl group, a benzo C4-6 cycloalkenyl group, a benzo C4-6 cycloalkynyl group, and a hydroxyphenyl group;

[0029] The substitution refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of halogen, silicon (-SiR3), cyano, hydroxyl, mercapto, amino, carboxyl, phenyl ether, phenyl thioether, C1-C4 ester, C1-C4 alkyl, halo-C1-C4 alkyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-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);

[0030] Wherein, R3 is selected from the following group:

[0031] Preferably, R5 is a group selected from the group consisting of vinyl, styryl, ethynyl, phenylethynyl, benzocyclobutenyl, vinylbenzocyclobutenyl, trifluorovinylphenyl ether, cyano, epoxy, cyanate, and isocyanate.

[0032] In another preferred embodiment, R1, R2, R3, and R4 are each independently selected from the following groups: 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 phenyl, and phenyl substituted with halogenated C1-C4 alkyl.

[0033] In another preferred embodiment, R1, R2, R3, and R4 are each independently selected from the following group: methyl, ethyl, propyl, trifluoropropyl, phenyl, 4-trifluoromethylphenyl, and 3,5-bistrifluoromethylphenyl.

[0034] In another preferred embodiment, n1 and n2 satisfy n1:(n1+n2) is (0.3-1):1; preferably (0.3-0.6):1.

[0035] In another preferred embodiment, R3 and R4 are both methyl, and R5 is

[0036] In another preferred embodiment, R3 and R4 are both methyl, and R5 is

[0037] In another preferred embodiment, R3 and R4 are both methyl, and R5 is

[0038] In another preferred embodiment, each substituent is a corresponding specific group in the compound in the examples.

[0039] In another preferred embodiment, the modified polymer has a monomer structure selected from the following group:

[0040] In a second aspect of the present invention, a method for preparing the modified polymer according to the first aspect of the present invention is provided, comprising the following steps:

[0041] In an inert solvent, in the presence of a catalyst, a polymer represented by the following formula (II) and a silane compound / siloxane compound containing a crosslinkable group represented by the following formula (III) are reacted to obtain a modified polymer represented by the following formula (I);

[0042] in,

[0043] n0 is 1 to 2000, and n0 and n3 satisfy n0: (n0 + n3) = (0.01 to 1): 1;

[0044] n4 is an integer from 0 to 12;

[0045] Each R1 and R2 is independently selected from the following group: H, a substituted or unsubstituted group selected from the following group: 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 cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C 2-C6 alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, urea, aminoester, isocyanate (-N=C=O), cyanate (-O-CN);

[0046] R3, R4 and R5 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, 3-7 membered cycloalkyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylamino, C2-C6 alkenylamino, C2-C6 Alkynylamino, C6-C10 aryl, C6-C10 aryloxy, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclyl, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl (-Ph-OH), urea, aminoester, -CO-NH-(C1-C4 alkyl), isocyanate, cyanate;

[0047] The substitution refers to that one or more hydrogen atoms on the group are replaced by a substituent selected from the group consisting of halogen, silicon (-SiR3), cyano, hydroxyl, 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, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, -CO-NH-(C1-C4 alkyl); and phenyl having 1-3 substituents selected from the group consisting of halogen, cyano, hydroxy, mercapto, amino, carboxyl, C1-C4 alkyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-C2-C4 alkynyl, isocyanate, cyanate;

[0048] Wherein, the monomer structure represented by the formula I contains m unsaturations, and m is 2-10;

[0049] Alternatively, in the monomer structure shown in Formula I wherein p cross-linkable groups or bonds are contained, and p is 1-10, wherein the cross-linkable groups or bonds are selected from the following group: cyano group (CN), hydroxyl group (-OH), thiol group (-SH), amino group (-NH2), carboxyl group (-COOH), carbamate group (-OC(O)-NH-), urea group (-NH-C(O)-NH-), ether bond (-O-), thioether bond (-S-), ester bond (-C(O)O-), alkenyl group, alkynyl group, phenyl group, heterocyclic group, cycloalkenyl group, cycloalkynyl group, isocyanate group, and cyanate group.

[0050] In another preferred embodiment, the molecular weight of the polymer of formula (II) is 500 to 100,000 g / mol.

[0051] In another preferred embodiment, the inert solvent is selected from the following group: C 1-10 Alkane solvents, C 6-12 Aromatic hydrocarbon solvents, or combinations thereof; preferably, dichloromethane, chloroform, dichloroethane, trichloroethane, n-hexane, cyclohexane, chlorobenzene, toluene, xylene, trimethylbenzene, or combinations thereof.

[0052] In another preferred embodiment, the catalyst is selected from the group consisting of chloroplatinic acid, chloroplatinic acid-isopropyl alcohol solution, methylvinylsiloxane platinum complex, Karstedt catalyst, or a combination thereof.

[0053] In another preferred embodiment, the reaction time is 1-25 h; preferably 2-20 h; more preferably 3-17 h.

[0054] In another preferred embodiment, the preparation method of the modified polymer specifically comprises the following steps: adding a polymer of formula (II) and a silane compound containing a crosslinkable group represented by formula (III) to an inert solvent, heating, adding a catalyst, and stirring the reaction to obtain a modified polymer represented by formula (I).

[0055] In another preferred embodiment, the reaction further comprises a post-treatment step: after the reaction is completed, filtering, settling, and drying to obtain the modified polymer represented by formula (I).

[0056] In another preferred embodiment, the method has the following characteristics:

[0057] (a) the molar ratio of the polymer of formula (II) to the silane compound containing a crosslinkable group represented by formula (III) is 1:(0.01-2); preferably 1:(0.2-0.8), and more preferably 1:(0.3-0.6);

[0058] (b) the molar volume ratio of the crosslinkable group-containing silane compound represented by formula (III) to the inert solvent is 0.05-0.5 mol / L, preferably 0.06-0.3 mol / L; and / or

[0059] (c) the mass molar ratio of the catalyst to the crosslinkable group-containing silane compound represented by formula (III) is 0.025-0.25 g / mol, preferably 0.05-0.2 g / mol; and / or

[0060] (d) The reaction temperature is 30-160°C; preferably 50-150°C; more preferably 60-130°C.

[0061] In the third aspect of the present invention, a silane compound / siloxane compound containing a crosslinkable group of formula (III) is provided.

[0062] Wherein, R1, R2, R3, R4 and R5 are as described in the first aspect of the present invention.

[0063] In another preferred embodiment, n4 is 0, R3 and R4 are both methyl, and R5 is

[0064] In another preferred embodiment, n4 is 0, R3 and R4 are both methyl, and R5 is

[0065] In another preferred embodiment, n4 is 0, R3 and R4 are both methyl, and R5 is

[0066] In another preferred embodiment, the silane compound containing a crosslinkable group described in formula (III) is

[0067] In another preferred embodiment, the silane compound containing a crosslinkable group described in formula (III) is

[0068] In another preferred embodiment, the silane compound containing a crosslinkable group described in formula (III) is

[0069] In the fourth aspect of the present invention, a cured product is provided, which is obtained by a cross-linking reaction of a curing raw material, wherein the curing raw material is the modified polymer described in the first aspect of the present invention, or a blend of the modified polymer described in the first aspect of the present invention and other curable monomers or polymers.

[0070] In another preferred embodiment, the cross-linking reaction is a reaction involving cross-linkable groups or bonds.

[0071] 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 ether, polytetrafluoroethylene, polyolefin, epoxy resin, cyanate resin, bismaleimide resin, or a combination thereof.

[0072] In another preferred embodiment, the mass fraction of the modified polymer described in the first aspect of the present invention in the curing raw material is 10%-100%, preferably 30%-100%, and more preferably 50%-100%.

[0073] In another preferred embodiment, the cured product is a polymer having a three-dimensional network structure obtained by a cross-linking reaction.

[0074] In another preferred embodiment, the cured product is a resin.

[0075] In another preferred embodiment, the cross-linking degree of the cured product is 50%-100%, preferably 70%-100%.

[0076] In another preferred embodiment, the cured product has one or more of the following characteristics:

[0077] (i) a dielectric constant of 2.3 to 2.7 (10 GHz), preferably 2.3 to 2.5;

[0078] (ii) Dielectric loss is 3.0×10 -4 ~2.0×10 -3 (10GHz), preferably 3.0~8.0×10 -4 ;

[0079] (iii) a glass transition temperature of 200 to 420°C, preferably 300 to 400°C;

[0080] (iv) a thermal expansion coefficient of 60 to 120 ppm / °C (room temperature to 300°C), preferably 70 to 110 ppm / °C; and / or

[0081] (v) Water absorption rate is 0.05 to 0.20% (after immersion in boiling water for 12 to 48 hours).

[0082] In a fifth aspect of the present invention, there is provided a method for preparing the cured product according to the fourth aspect of the present invention, comprising the following steps:

[0083] Under the protection of an inert gas, the curing raw material is heated and cured to obtain a cured product; wherein the curing raw material is the modified polymer described in the first aspect of the present invention, or a blend of the modified polymer described in the first aspect of the present invention and other heat-curable monomers or polymers.

[0084] In another preferred embodiment, the inert gas is selected from the following group: nitrogen and argon.

[0085] In another preferred embodiment, the heat curing is direct heat curing, or curing is performed by dissolving the curing raw material in an organic solvent to obtain a cured product.

[0086] In another preferred embodiment, the organic solvent is selected from the following group: C 1-10 Alkane solvents, C 6-12 Aromatic hydrocarbon solvents, ether solvents, amide solvents, sulfone solvents, or combinations thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or combinations thereof.

[0087] In another preferred embodiment, the heat curing is carried out at 100-350°C, preferably 150-300°C.

[0088] In another preferred embodiment, the heat curing is programmed temperature curing.

[0089] In another preferred embodiment, the heat curing comprises: curing at 190-220° C. for 1-6 hours, then curing at 220-250° C. for 3-6 hours, and then curing at 250-300° C. for 0.5-3 hours;

[0090] In another preferred embodiment, the heat curing comprises: curing at 190-220° C. for 1-4 hours, then curing at 220-250° C. for 4-6 hours, and then curing at 250-300° C. for 1-3 hours.

[0091] In the sixth aspect of the present invention, a product is provided, which is prepared from the modified polymer described in the first aspect of the present invention or the cured product described in the fourth aspect of the present invention, or includes the modified polymer described in the first aspect of the present invention or the cured product described in the fourth aspect of the present invention.

[0092] In another preferred embodiment, the product is obtained by heating and curing a preform of the curing raw material.

[0093] In another preferred embodiment, the preform is formed by a molding process selected from the group consisting of: casting, solution spin coating, or solution drop coating.

[0094] In another preferred embodiment, the solution spin coating or solution drop coating comprises the steps of: dissolving the curing raw material or the prepolymer of the curing raw material in a second inert solvent to form a solution, and then performing spin coating or drop coating;

[0095] The prepolymer is a polymer obtained by dissolving a curing raw material in a second inert solvent and then heating and cross-linking.

[0096] In another preferred embodiment, the second inert solvent is selected from the following group: C 1-10 Alkane solvents, C 6-12 Aromatic hydrocarbon solvents, ether solvents, amide solvents, sulfone solvents, or combinations thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or combinations thereof.

[0097] In another preferred embodiment, the product is a substrate and a thin film formed by the solidified raw material coated on the surface of the substrate.

[0098] In another preferred embodiment, the product is selected from the following group: low dielectric film substrate material, low dielectric film, low dielectric constant matrix resin, low dielectric constant packaging material, high frequency low dielectric constant material, low dielectric constant photo-patterned material.

[0099] In the seventh aspect of the present invention, a use of the product described in the sixth aspect of the present invention is provided for preparing a high-frequency, low-dielectric constant material, wherein the high-frequency, low-dielectric constant material is selected from the following group: a low-dielectric film substrate material, a low-dielectric film, a low-dielectric constant matrix resin, a low-dielectric packaging material, and a low-dielectric constant photo-patterned material.

[0100] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features described in detail below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be listed here one by one. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 shows the DSC curves of polybutadiene with different benzocyclobutene side chain contents (10℃ / min, N2)

[0102] Figure 2 shows the TGA curves of polybutadiene with different benzocyclobutene side chain contents (5°C / min, N2)

[0103] FIG3 is a graph showing the change in water absorption of polybutadiene with different benzocyclobutene side chain contents after curing. DETAILED DESCRIPTION

[0104] After extensive and in-depth research, the inventors have developed a heat-curable hydrocarbon resin for the first time. This hydrocarbon resin has a 1,2-polybutadiene backbone with silanes containing crosslinkable groups attached to its side chains. By adjusting the content of double bonds in the backbone's side chains, a material with a low dielectric constant and low dielectric loss is obtained. This material exhibits a low dielectric constant and extremely low dielectric loss at 10 GHz, while also possessing high modulus, low water absorption, and good heat resistance. It can be used as a low-dielectric-constant matrix resin or encapsulation material in fields such as high-frequency communications, microelectronics, and aerospace. Based on this, the inventors completed the present invention.

[0105] the term

[0106] 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.

[0107] As used herein, the terms "comprising" or "including" may be open, semi-closed, or closed. In other words, the terms also include "consisting essentially of" or "consisting of."

[0108] 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.

[0109] In the present invention, "C1-C6 alkyl" refers to a straight or branched chain alkyl group containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, tert-pentyl, or the like. "C1-C4 alkyl" has a similar meaning.

[0110] In the present invention, the term "C2-C6 alkenyl" refers to a straight chain or branched alkenyl group having 2 to 6 carbon atoms and containing one double bond, including but not limited to ethenyl, propenyl, butenyl, isobutenyl, pentenyl and hexenyl.

[0111] In the present invention, the term "C2-C6 alkynyl" refers to a straight chain or branched alkynyl group having 2 to 6 carbon atoms and containing one triple bond, including but not limited to ethynyl, propynyl, butynyl, isobutynyl, pentynyl and hexynyl.

[0112] 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 but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. "C3-C4 cycloalkyl" has a similar meaning.

[0113] In the present invention, the term "C1-C6 alkoxy" refers to a straight or branched alkoxy group (C1-C6 alkyl-O-) having 1 to 6 carbon atoms, including but not limited to methoxy, ethoxy, propoxy, isopropoxy and butoxy, etc. Preferably, it is a C1-C4 alkoxy group.

[0114] In the present invention, the term "3-7 membered cycloalkoxy" refers to a cyclic group having 1 oxygen atom and 2-6 ring atoms, including but not limited to cyclopropyl, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and the like.

[0115] In the present invention, the term "C2-C6 alkenyloxy" refers to a straight or branched alkenyloxy group (C2-C6 alkenyl-O-) having 2 to 6 carbon atoms, including but not limited to vinyloxy, propenyloxy, isopropenyloxy and butenyloxy, etc. Preferably, it is C2-C4 alkenyloxy.

[0116] In the present invention, the term "C2-C6 alkynyloxy" refers to a straight or branched alkynyloxy group (C2-C6 alkynyl-O-) having 1 to 6 carbon atoms, including but not limited to ethynyloxy, propynyloxy, isopropynyloxy and butynyloxy, etc. Preferably, it is C2-C4 alkynyloxy.

[0117] In the present invention, the term "C1-C6 alkylthio" refers to a straight or branched chain alkylthio group (C1-C6 alkyl-S-) having 1 to 6 carbon atoms, including but not limited to methylthio, ethylthio, propylthio, isopropylthio and butylthio, etc. Preferably, it is a C1-C4 alkylthio group.

[0118] In the present invention, the term "C2-C6 alkenylthio" refers to a straight or branched chain alkenylthio group (C2-C6 alkenyl-S-) having 1 to 6 carbon atoms, including but not limited to vinylthio, propenylthio, isopropenylthio and butenylthio. Preferably, it is C2-C4 alkenylthio.

[0119] In the present invention, the term "C2-C6 alkynylthio" refers to a straight or branched chain alkynylthio group (C2-C6 alkynyl-S-) having 1 to 6 carbon atoms, including but not limited to ethynylthio, propynylthio, isopropynylthio and butynylthio. Preferably, it is C2-C4 alkynylthio.

[0120] In the present invention, the term "plurality" refers to 1-7.

[0121] In the present invention, the term 1 to 6 refers to 1, 2, 3, 4, 5 or 6. Other similar terms have similar meanings.

[0122] The term "ester group" has a -C(O)-O-R' or R'-C(O)-O- structure, wherein R' independently represents hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, heteroaryl, heterocyclyl, as defined above.

[0123] The term "urea group" refers to

[0124] The term "C1-C6 alkylamino" refers to a group having a -C1-C6 alkyl-NH2 or C1-C6 alkyl-NH- structure, and other groups have similar definitions.

[0125] As used herein, the term "aryl," as a group or as part of another group, refers to a conjugated hydrocarbon ring system having 6 to 10 carbon atoms. For the purposes of this invention, an aryl group can be monocyclic or bicyclic; it can be a bridged, spirocyclic, or paracyclic ring structure. Examples of aryl groups include, but are not limited to, phenyl and naphthyl.

[0126] In the present invention, the term "C6-C10 aryloxy group" refers to a group having a C1-C6 aryl-O- structure.

[0127] As used herein, the term "5-10 membered heteroaryl having 1-3 heteroatoms independently selected from N, S, and O" refers to a cyclic aromatic group having 5-10 atoms, 1-3 of which are heteroatoms selected from the group consisting of N, S, and O. It may be a monocyclic or condensed ring. Specific examples include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1,2,3)-triazolyl and (1,2,4)-triazolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, and oxazolyl.

[0128] As used herein, the term "5-6 membered heterocyclyl" refers to a cyclic structure having 5-6 ring atoms, 1-3 of which are heteroatoms independently selected from N, S and O.

[0129] In the present invention, the term "substituted" refers to the replacement of one or more hydrogen atoms on a specific group with a specific substituent. The specific substituents are the substituents described above or the substituents appearing in the examples. Unless otherwise specified, a substituted group may have a substituent selected from the specified group at any substitutable position of the group, and the substituents may be the same or different at each position. It will be understood by those skilled in the art that the combinations of substituents contemplated by the present invention are those that are stable or chemically feasible. Such substituents include, but are not limited to, deuterium, halogen, hydroxyl, cyano, amino, alkylamino, carbonyl, C1-6 alkyl, C1-6 alkoxy, C3-6 cycloalkyl, halo-C1-6 alkyl, halo-C1-6 alkoxy, halo-C3-6 cycloalkyl, halo-alkylamino, 3-7 membered heterocyclyl, aryl, heteroaryl, C2-6 acyl, C2-6 ester, C2-6 alkynyl, C2-6 alkenyl, and the like.

[0130] The compounds of the present application can 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 specific embodiments with other chemical synthesis methods, and equivalent replacement methods well known to those skilled in the art. Preferred embodiments include but are not limited to the examples of the present application.

[0131] As used herein, the "crosslinkable curing group" refers to a group or bond that can undergo a crosslinking reaction and / or a group having unsaturation.

[0132] As used herein, the "silane compound" includes "siloxane compound".

[0133] Silane / siloxane containing a crosslinkable group represented by formula (III)

[0134] The crosslinkable group-containing silane / siloxane used in the present invention may be known in the art, or may be commercially available, or may be prepared by conventional synthesis methods in the art.

[0135] Specifically, the present invention also provides a method for preparing a silane / siloxane containing a crosslinkable group represented by formula (III), the preparation method comprising the following steps:

[0136] Method (1-1): Under the protection of an inert gas, a hydrogen-containing chlorosilane or a hydrogen-containing siloxane B is reacted with a halogenated benzocyclobutene, a halogenated vinylbenzocyclobutenyl or a halogenated phenyl trifluorovinyl ether A to obtain a silane containing benzocyclobutene, vinylbenzocyclobutenyl or trifluorovinyl ether, i.e., a compound of formula (III), wherein n4=0, X is a halogen, and R is a C1-6 alkyl group;

[0137] Method (2-1): Under the protection of an inert gas, a halogenated benzocyclobutene, a halogenated vinylbenzocyclobutenyl, or a halogenated phenyl trifluorovinyl ether A is reacted with Mg to obtain a Grignard reagent C, which is then reacted with a hydrogen-containing chlorosilane or a hydrogen-containing siloxane B to obtain a silane containing benzocyclobutene, vinylbenzocyclobutenyl, or phenyl trifluorovinyl ether, i.e., a compound of formula (III), wherein X is a halogen, R is a C1-6 alkyl, and n4=0;

[0138] Method (1-2): Under the protection of an inert gas, a siloxane D containing benzocyclobutene, a halogenated vinylbenzocyclobutenyl group or a phenyl trifluorovinyl ether is reacted with a disiloxane E to obtain a silane containing benzocyclobutene, a vinylbenzocyclobutenyl group or a phenyl trifluorovinyl ether, i.e., a compound of formula (III), wherein R is a C1-6 alkyl group, n4≠0, and n4 is a positive integer of 1-12.

[0139] Method (2-2): Under the protection of an inert gas, a siloxane D containing benzocyclobutene, vinylbenzocyclobutenyl or phenyl trifluorovinyl ether is reacted with a disiloxane E to obtain a silane containing benzocyclobutene, vinylbenzocyclobutenyl or phenyl trifluorovinyl ether, i.e., a compound of formula (III), wherein R is a C1-6 alkyl group, n4≠0, and n4 is a positive integer of 1-12.

[0140] The heat-curable low dielectric constant polymer of the present invention

[0141] The present invention provides a heat-curable low dielectric constant polymer, the monomer of which has a structure shown in the following formula I:

[0142] In the formula, the definitions of each group and symbol are as described in the specification.

[0143] The heat-curable polybutadiene of the present invention exhibits high heat resistance (T5d>420°C), low water absorption (as low as 0.05%), high glass transition temperature (Tg>400°C), low thermal expansion coefficient (room temperature to 300°C, CTE as low as 72ppm / °C), and good dielectric properties (dielectric constant as low as 2.32, dielectric loss as low as 3.4×10 -4 ).

[0144] The polymer of the present invention can also be used as a modifier in other materials in need to improve the dielectric properties of the materials.

[0145] The heat-curable polymer of the present invention can be prepared using conventional synthetic methods in the art. Specifically, the polymer of the present invention is cross-linked by a polymer represented by formula (II) and a silane compound / siloxane compound containing a cross-linkable group represented by formula (III) under the action of a catalyst.

[0146] The definitions of the groups and symbols are as described in the specification.

[0147] Preferably, the catalyst is selected from the group consisting of chloroplatinic acid, chloroplatinic acid-isopropanol solution, methylvinylsiloxane platinum complex, Karstedt catalyst, or a combination thereof.

[0148] The molecular weight of the polymer of formula (II) is 500 to 100,000 mW.

[0149] The crosslinkable group-containing silane compound / siloxane compound represented by formula (III) contains at least one crosslinkable group. The crosslinkable group refers to a group or chemical bond that can undergo a crosslinking reaction (e.g., thermal crosslinking), including but not limited to a cyano group (CN), a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH2), a carboxyl group (-COOH), a carbamate group (-OC(O)-NH-), a urea group (-NH-C(O)-NH-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-C(O)O-), an alkenyl group, an alkynyl group, a phenyl group, a heterocyclic group, a cycloalkenyl group, or a cycloalkynyl group; and / or the compound represented by formula III has 1 to 10 degrees of unsaturation; preferably, 2 to 6 degrees of unsaturation.

[0150] Cured product

[0151] The present invention also provides a cured product, which is a polymer having a three-dimensional network structure obtained by a crosslinking reaction. The cured product is obtained by crosslinking a curing raw material. Generally speaking, the curing raw material is the polymer described in the first aspect of the present invention, and may also include other heat-curable monomers or polymers known in the art.

[0152] Preferably, other heat-curable monomers or polymers known in the art include low dielectric polyimide, polyphenylene ether, polytetrafluoroethylene, or a combination thereof.

[0153] Preferably, the other thermally curable monomers or polymers known in the art are low dielectric polymers.

[0154] Preferably, the mass fraction of the polymer in the curing raw material is 10%-100%, more preferably 30%-100%, and more preferably 50%-100%.

[0155] Preferably, the cured product is a resin.

[0156] Preferably, the degree of cross-linking of the cured product is 50%-100%, preferably 70%-100%.

[0157] The cured product of the present invention is infusible and insoluble, and has excellent low dielectric properties, excellent thermal mechanical properties, low water absorption and excellent surface smoothness, especially high frequency low dielectric properties.

[0158] Specifically, the cured product has one or more of the following characteristics:

[0159] (i) a dielectric constant of 2.3 to 2.7 (10 GHz), preferably 2.3 to 2.5;

[0160] (ii) dielectric loss of 3.0×10-4 to 2.0×10-3 (10 GHz), preferably 3.0 to 8.0×10-4;

[0161] (iii) a glass transition temperature of 200 to 420°C, preferably 300 to 400°C;

[0162] (iv) a thermal expansion coefficient of 60 to 120 ppm / °C (room temperature to 300°C), preferably 70 to 110 ppm / °C;

[0163] (v) Water absorption rate is 0.05 to 0.20% (after immersion in boiling water for 12 to 48 hours).

[0164] In addition, the present invention also provides a method for preparing a solidified product, which specifically comprises the following steps:

[0165] Under the protection of an inert gas, the curing raw material is heated and cured to obtain a cured product; wherein the curing raw material is the polymer described in the first aspect of the present invention, or a blend of the polymer described in the first aspect of the present invention and other heat-curable monomers or polymers.

[0166] The inert gas is a commonly used inert gas in the art, preferably nitrogen, argon, or a combination thereof.

[0167] Specifically, the "heat curing" in the present invention includes directly curing the curing raw material by heat and curing it, and curing it by dissolving the curing raw material in an organic solvent, thereby obtaining a cured product.

[0168] Preferably, the organic solvent is selected from the following group: C1-10 alkane solvents, C6-12 aromatic hydrocarbon solvents, ether solvents, amide solvents, sulfone solvents, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or a combination thereof.

[0169] Preferably, the heat curing is programmed temperature curing; the curing temperature is 100-350°C, preferably 150-300°C.

[0170] Preferably, the heat curing comprises: curing at 190-220°C for 1-6 hours, then curing at 220-250°C for 3-6 hours, and then curing at 250-300°C for 0.5-3 hours;

[0171] More preferably, the heat curing comprises: curing at 190-220° C. for 1-4 hours, then curing at 220-250° C. for 4-6 hours, and then curing at 250-300° C. for 1-3 hours.

[0172] use

[0173] The present invention also provides a use of the polymer described in the first aspect of the present invention and the cured product described in the third aspect of the present invention for preparing a high-frequency, low-dielectric constant material, wherein the high-frequency, low-dielectric constant material is selected from the following group: a low-dielectric film substrate material, a low-dielectric film, a low-dielectric constant matrix resin, a low-dielectric packaging material, and a low-dielectric constant photo-patterned material.

[0174] Specifically, the solidified raw material of the present invention can be preformed and then heated and solidified to obtain the solidified raw material.

[0175] Preforming refers to applying the polymer of the present invention as a coating layer to a desired surface or pouring it into a desired shape by means of casting, spin coating, or drop coating. The curing raw material can be preformed directly, or the curing raw material can be dissolved in a second inert solvent to prepare a prepolymer, and the prepolymer can be used for preforming.

[0176] Preferably, the second inert solvent is selected from the following group: C1-10 alkane solvents, C6-12 aromatic hydrocarbon solvents, ether solvents, amide solvents, sulfone solvents, or a combination thereof; preferably, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or a combination thereof.

[0177] Compared with the prior art, the main advantages of the present invention include:

[0178] (1) The present invention provides a thermosetting polymer having a structure shown in Formula I with excellent film-forming properties and a low thermal crosslinking temperature.

[0179] (2) The present invention obtains thermosetting polymers having a structure shown in Formula I with different contents of thermosetting side groups by performing a simple hydrosilylation reaction on 1,2-polybutadiene. The preparation method is simple, the reaction conditions are mild, and the polymers are suitable for large-scale industrial production.

[0180] (3) After curing, the thermosetting polymer of the present invention exhibits high heat resistance (T5d>420°C), low water absorption (as low as 0.05%), high glass transition temperature (Tg>400°C), low thermal expansion coefficient (room temperature to 300°C, CTE as low as 72ppm / °C), and good dielectric properties under high frequency conditions of 10GHz (dielectric constant as low as 2.32, dielectric loss as low as 3.4×10 -4 ).

[0181] (4) The thermosetting polymer of the present invention can be directly thermally cured to produce a sheet, or can be blended with a filler to obtain a low dielectric constant material with excellent performance.

[0182] (5) The thermosetting polymer of the present invention is a new type of thermosetting hydrocarbon resin, which can be used as a high-performance matrix resin or packaging material in the fields of high-frequency communications, large-scale integrated circuits, microelectronics industry, aerospace, etc.

[0183] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples, where specific conditions are not specified, are generally based on the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0184] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the methods of the present invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0185] Example 1: Benzocyclobutene silyl hydride

[0186] Under nitrogen, a 250 mL dry three-necked flask was charged with 150.0 mmol of magnesium turnings, 150 mL of tetrahydrofuran, 150.0 mmol of dimethylsilyl chloride, and a small pellet of I2 (approximately 30 mg). Then, 100.0 mmol of 4-bromobenzocyclobutene was slowly added dropwise. Heat was initiated to maintain a slight boil. After the addition was complete, the reaction was allowed to proceed overnight at room temperature. After the reaction, n-hexane was added, the salts were filtered off, and the solvent was concentrated and distilled under reduced pressure (external temperature 80°C, internal temperature 61°C) to obtain 14.08 g of compound S1, a colorless, transparent liquid, for an 87% yield. 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). 13 C 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).

[0187] Example 2: Vinylbenzocyclobutenylsilane hydride

[0188] Under nitrogen, a 1000mL dry three-necked flask was charged with 200mL of acetonitrile, 639.7mmol of 4-bromobenzocyclobutene, 767.7mmol of vinyldimethylethoxysilane, 31.9mmol of palladium acetate, 127.9mmol of tri-(2-methylphenyl)phosphine, and 1407.4mmol of triethylamine. Nitrogen was bubbled through the flask for 3 hours, and the mixture was heated to 105°C and refluxed overnight. After the reaction, the mixture was filtered, the solvent was dried, and the mixture was used directly in the next step. In another 500mL dry three-necked flask, 50mL of anhydrous THF and 100.0mmol of S2 were added. The mixture was placed in an ice bath, and 100.0mmol of LiAlH4 was added. The temperature was slowly raised to room temperature and the reaction continued for 5 hours. After the reaction, a small amount of water was added to quench the mixture in an ice bath, and the mixture was extracted with petroleum ether. The mixture was dried over anhydrous sodium sulfate, filtered, dried, and evaporated under reduced pressure to yield 12.2g of compound S3 as a colorless, transparent liquid in a 65% yield. 1 H 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); 13 C 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.

[0189] Example 3: Synthesis of polybutadiene PB-g-B5 containing 5% benzocyclobutene side chains

[0190] Under nitrogen, 40.0 mmol of polymer II (m:n = 9:1), 10 mL of mesitylene, and 2.4 mmol of compound S1 were added to a 100 mL two-necked flask. The temperature was slowly raised to 120°C, and 0.1 mL of H2PtCl6 solution (10 mg / mL in isopropanol) was added. The reaction was continued at 120°C for 3 h. After terminating the reaction, the solvent was removed under reduced pressure. Neutral alumina was added to the funnel and the catalyst was filtered out. Finally, the solution was precipitated in methanol three times to obtain 2.19 g of colorless polymer PB-g-B5 (80% yield). 1 H 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). 13 C NMR(151MHz,Chloroform-d)δ146.95,145.61,144.40–141.99(m),137.80,131.95,127.46,1 22.00,115.21–113.90(m),39.09–38.83(m),30.06,29.91,18.10,13.14,1.17,0.15,-2.68. 29 Si NMR(119MHz,Chloroform-d)δ-1.90.

[0191] Example 4: Polybutadiene PB-gB containing 30% benzocyclobutene side chains 30 Synthesis

[0192] Under nitrogen, 30.0 mmol of polymer II (m:n = 9:1), 30 mL of mesitylene, and 10.0 mmol of compound S1 were added to a 100 mL two-necked flask. The temperature was slowly raised to 120°C, and 0.1 mL of H2PtCl6 solution (10 mg / mL in isopropanol) was added. The reaction was continued at 120°C for 3 h. After stopping the reaction, the solvent was removed under reduced pressure. Neutral alumina was added to the funnel and the catalyst was filtered out. Finally, the solution was precipitated in methanol three times to obtain a colorless polymer PB-gB. 30 A total of 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). 13 C NMR(151MHz,Chloroform-d)δ146.95,145.61,144.40–141.99(m),137.80,131.95,127.46,1 22.00,115.21–113.90(m),39.09–38.83(m),30.06,29.91,18.10,13.14,1.17,0.15,-2.68. 29 Si NMR(119MHz,Chloroform-d)δ-1.94.

[0193] Example 5: Polybutadiene PB-gB containing 60% benzocyclobutene side chains 60 Synthesis

[0194] Under nitrogen, 20.0 mmol of polymer II (m:n = 9:1), 20 mL of mesitylene, and 13.0 mmol of compound S1 were added to a 50 mL two-necked flask. The temperature was slowly raised to 120°C, and 0.1 mL of H2PtCl6 solution (10 mg / mL in isopropanol) was added. The reaction was continued at 120°C for 9 h. After stopping the reaction, the solvent was removed under reduced pressure. Neutral alumina was added to the funnel and the catalyst was filtered out. Finally, the solution was precipitated in methanol three times to obtain a colorless polymer PB-gB. 60 A total of 2.84g, yield: 90%. 1 H 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),137.79,131.95,127.45,122.01,114.7 9–144.03(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. 29 Si NMR(119MHz,Chloroform-d)δ-2.02.

[0195] Example 6: Polybutadiene PB-gB containing 100% benzocyclobutene side chains 100 Synthesis

[0196] Under nitrogen, 20.0 mmol of polymer II (m:n = 9:1), 30 mL of mesitylene, and 16.0 mmol of compound S1 were added to a 100 mL two-necked flask. The temperature was slowly raised to 120°C, and 0.1 mL of H2PtCl6 solution (10 mg / mL in isopropanol) was added. The reaction was continued at 120°C for 19 hours. After stopping the reaction, the solvent was removed under reduced pressure. Neutral alumina was added to the funnel and the catalyst was filtered out. Finally, the solution was precipitated in methanol three times to obtain a colorless polymer PB-gB. 100 A total of 4.0 g, yield: 89%. 1 H 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). 13 C 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. 29 Si NMR(119MHz,Chloroform-d)δ-2.07.

[0197] Example 7: Curing of Thermosetting Polybutadiene PB-g-B5 and Properties of Its Cured Products

[0198] The target polymer PB-g-B5 prepared in Example 2 was placed in a tube furnace, and bubbles were removed at 150°C. The temperature was raised to 210°C and cured for 3 h, 240°C for 3 h, and 270°C for 2 h to obtain the cured resin Cured-PB-g-B5.

[0199] The solidified sample was polished into a uniform disc and its dielectric properties were tested. The results showed that the dielectric constant was 2.32 and the dielectric loss was 7.3×10 -4 The TGA test results show that the 5% thermal weight loss temperature (T 5d ) is 427°C. DMA testing results indicate that the cured resin has a glass transition temperature of 181°C. CTE testing reveals a coefficient of thermal expansion of 117 ppm / °C from room temperature to 200°C. As shown in Figure 3, after immersing cured-PB-g-B5 in boiling water for 48 hours, its water absorption was found to be 0.18%.

[0200] Example 8: Thermosetting polybutadiene PB-gB 30 Study on the curing of bismuth and the properties of its corresponding cured products

[0201] Take the target polymer PB-gB prepared in Example 3 30 Place in a tube furnace, remove bubbles at 150℃, heat to 210℃ and cure for 3h, 240℃ and 270℃, and cure for 2h to obtain cured-PB-gB resin. 30 .

[0202] The solidified sample was polished into a uniform disc and its dielectric properties were tested. The results showed that the dielectric constant was 2.34 and the dielectric loss was 3.6×10 -4 The TGA test results show that the 5% thermal weight loss temperature (T 5d ) is 437℃. DMA test results show that the glass transition temperature of the cured resin is 209℃. CTE test shows that the thermal expansion coefficient is 88ppm / ℃ in the range of room temperature to 200℃. As shown in Figure 3, the cured-PB-gB 30 After soaking in boiling water for 48 hours, the water absorption rate was tested to be 0.05%.

[0203] Example 9: Thermosetting polybutadiene PB-gB 60 Study on the curing of bismuth and the properties of its corresponding cured products

[0204] Take the target polymer PB-gB prepared in Example 4 60Place in a tube furnace, remove bubbles at 150℃, heat to 210℃ and cure for 3h, 240℃ and 270℃, and cure for 2h to obtain cured-PB-gB resin. 60 .

[0205] The solidified sample was polished into a uniform disc and its dielectric properties were tested. The results showed that the dielectric constant was 2.37 and the dielectric loss was 8.3×10 -4 The TGA test results show that the 5% thermal weight loss temperature (T 5d ) is 446℃. DMA test results show that the glass transition temperature of the cured resin is greater than 400℃. CTE test shows that the thermal expansion coefficient is 72ppm / ℃ in the range of room temperature to 300℃. As shown in Figure 3, the cured-PB-gB 60 After soaking in boiling water for 48 hours, the water absorption rate was tested to be 0.08%.

[0206] Example 10: Thermosetting polybutadiene PB-gB 100 Study on the curing of bismuth and the properties of its corresponding cured products

[0207] Take the target polymer PB-gB prepared in Example 5 100 Place in a tube furnace, remove bubbles at 150℃, heat to 210℃ and cure for 3h, 240℃ and 270℃, and cure for 2h to obtain cured-PB-gB resin. 100 .

[0208] The solidified sample was polished into a uniform disc and its dielectric properties were tested. The results showed that the dielectric constant was 2.41 and the dielectric loss was 1.10×10 -3 The TGA test results show that the 5% thermal weight loss temperature (T 5d ) is 453℃. DMA test results show that the glass transition temperature of the cured resin is greater than 400℃. CTE test shows that the thermal expansion coefficient is 81ppm / ℃ in the range of room temperature to 300℃. As shown in Figure 3, the cured-PB-gB 100 After soaking in boiling water for 48 hours, the water absorption rate was tested to be 0.17%.

[0209] discuss

[0210] The dielectric constants of the currently commonly used low-dielectric substrate materials do not differ much (2.0 to 3.5), but the dielectric loss has an order of magnitude difference (10 -2 ~10 -4 ), so the dielectric loss of low dielectric materials has a more important impact on high-frequency and high-speed circuits.

[0211] At present, the most commonly used low-dielectric substrate materials in high-frequency and high-speed circuits include polytetrafluoroethylene (PTFE), thermosetting polyphenylene ether (PPO) and hydrocarbon resin. Among them, PTFE is the most widely used in high-frequency and high-speed circuits because of its extremely low dielectric constant (2.2-2.6), dielectric loss (≤2×10 -3 ) and excellent thermal stability and flame retardancy, but PTFE also has obvious shortcomings. As a thermoplastic polymer, PTFE has relatively poor mechanical strength, and the high fluorine content also greatly reduces the bonding performance between the material and the conductor. It is difficult to process and expensive. Thermosetting PPO has more outstanding adhesion and mechanical properties than PTFE, and has more advantages in processability, but its dielectric constant (2.6 to 3.3) and dielectric loss (3×10 -3 ~7×10 -3 ) is difficult to meet higher requirements. As a resin with ultra-low polarity, hydrocarbon resin has a dielectric constant (2.2-2.5) and dielectric loss (2.5×10 -3 ~3.5×10 -3 ) is closer to PTFE and has a lower price, but has poorer thermal stability and a higher curing temperature.

[0212] The present invention starts from the molecular structure of 1,2-polybutadiene and utilizes a hydrosilylation reaction to introduce a heat-curable group on the vinyl group of its side chain to obtain a thermosetting polymer. After curing, the polymer provided by the present invention exhibits high heat resistance (T5d>420℃), low water absorption (as low as 0.05%), high glass transition temperature (Tg>400℃), low thermal expansion coefficient (room temperature to 300℃, CTE as low as 72ppm / ℃), and good dielectric properties under high frequency conditions of 10GHz (dielectric constant as low as 2.32, dielectric loss as low as 3.4×10 -4 ).

[0213] By adjusting the vinyl addition rate, the dielectric and mechanical properties of the material can be adjusted. In general, the higher the addition rate of the polymer, the better the mechanical properties and thermal stability after curing, while the dielectric constant has a slight increase or decrease. It is worth mentioning that when the content of the introduced heat-curable group is too low, the double bonds of the polybutadiene side chain cannot be completely cross-linked, and the dielectric loss of the polymer will increase significantly. When the content of the introduced benzocyclobutene group is 30% of the side chain double bonds, the lowest dielectric loss of 3.6×10 -4 , which is far superior to the currently known low-dielectric materials used in high-frequency and high-speed circuits.

[0214] All documents mentioned in this application are incorporated herein by reference, just as if each document were incorporated herein by reference individually. It should also be understood that after reading the above teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, and that such equivalents also fall within the scope of the claims appended hereto.

Claims

1. A curable modified polymer, characterized in that, The modified polymer has a monomer structure as shown in the following formula I: Among them, n1 and n2 satisfy n1:(n1 + n2)=(0.01 - 1):1; n1, n2 and n3 satisfy n1:(n1 + n2 + n3)=(0.01 - 1):1; n4 is an integer from 0 to 12; Each R1 and R2 is independently selected from the following group: H, a substituted or unsubstituted group selected from the following group: 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, 5-10 membered heteroaryl having 1-3 heteroatoms independently selected from N, O and S, benzo 5-6 membered heterocyclic group, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido, aminoester group, isocyanate group (-N = C = O), cyanate group (-O-CN); R3, R4 and R5 are independently selected from the following group: H, a substituted or unsubstituted group selected from the following group: 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, 5-10 membered heteroaryl having 1-3 heteroatoms independently selected from N, O and S, benzo 5-6 membered heterocyclic group, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl (-Ph-OH), ureido, aminoester group, -CO-NH-(C1-C4 alkyl), isocyanate group (-N = C = O), cyanate group (-O-CN); The substitution mentioned above means that one or more hydrogens on the group are substituted by substituents selected from the following group: halogen, silyl (-SiR3), cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), phenyl ether group (Ph-O-), phenyl sulfide group (Ph-S-), C1-C4 ester group, C1-C4 alkyl group, halogenated C1-C4 alkyl group, C2-C4 alkenyl group, halogenated C2-C4 alkenyl group, C2-C4 alkynyl group, halogenated C2-C4 alkynyl group, C3-C6 cycloalkyl group, C1-C6 alkoxy group, C2-C6 alkenyloxy group, C2-C6 alkynyloxy group, 3-7 membered cycloalkoxy group, C1-C6 alkylthio group, C2-C6 alkenylthio group, C2-C6 alkynylthio group, unsubstituted phenyl group, benzocyclo C3-6 alkyl group, benzocyclo C4-6 alkenyl group, benzocyclo C4-6 alkynyl group, -CO-NH-(C1-C4 alkyl group); and phenyl group having 1-3 substituents selected from the following group: halogen, cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), C1-C4 alkyl group, C2-C4 alkenyl group, halogenated C2-C4 alkenyl group, C2-C4 alkynyl group, halogenated C2-C4 alkynyl group, isocyanate group, cyanate group; Wherein, the monomer structure shown in Formula I contains m degrees of unsaturation, and m is 2-10; Alternatively, in the monomer structure represented by Formula I contains p crosslinkable groups or bonds, and p is 1-10. Among them, the crosslinkable groups or bonds are selected from the following group: cyano (CN), hydroxyl (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), urethane group (-O-C(O)-NH-), urea group (-NH-C(O)-NH-), ether bond (-O-), thioether bond (-S-), ester bond (-C(O)O-), alkenyl group, alkynyl group, phenyl group, heterocyclic group, cycloalkenyl group, cycloalkynyl group, isocyanate group, cyanate group.

2. The modified polymer according to claim 1, wherein, n4 is 0, R3 and R4 are each independently selected from the following group: H, C1-C6 alkyl group, halogenated C1-C6 alkyl group, C3-C6 cycloalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 alkylamino group, C1-C6 hydroxyalkyl group, phenyl group, halogenated phenyl group, phenyl group substituted by halogenated C1-C6 alkyl group; R5 is a group containing a crosslinkable group or bond and selected from the following groups; H, a substituted or unsubstituted group selected from the following groups: 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, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O and S, benzofused 5-6 membered heterocyclic group, benzofused C3-6 cycloalkyl, benzofused C4-6 cycloalkenyl, benzofused C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl, ureido, aminoester group, -CO-NH-(C1-C4 alkyl), isocyanate group, cyanate group; The said substitution means that one or more hydrogens on the group are substituted by substituents selected from the following groups: halogen, silyl (-SiR3), cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH2), carboxy (-COOH), phenyl ether group (Ph-O-), phenylthioether group (Ph-S-), C1-C4 ester group, C1-C4 alkyl, halo C1-C4 alkyl, C2-C4 alkenyl, halo C2-C4 alkenyl, C2-C4 alkynyl, halo 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, benzofused C3-6 cycloalkyl, benzofused C4-6 cycloalkenyl, benzofused C4-6 cycloalkynyl, -CO-NH-(C1-C4 alkyl); and phenyl having 1-3 substituents selected from the following groups: halogen, cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH2), carboxy (-COOH), C1-C4 alkyl, C2-C4 alkenyl, halo C2-C4 alkenyl, C2-C4 alkynyl, halo C2-C4 alkynyl; Preferably, R5 is a group containing a crosslinkable group or bond and selected from the following groups; H, a substituted or unsubstituted group selected from the following groups: 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, benzofused 5-6 membered heterocyclic group, benzofused C3-6 cycloalkyl, benzofused C4-6 cycloalkenyl, benzofused C4-6 cycloalkynyl, hydroxyphenyl; The substitution refers to that one or more hydrogens on the group are substituted by substituents selected from the following group: halogen, silyl (-SiR3), cyano, hydroxyl, mercapto, amino, carboxyl, phenyl ether group, phenyl sulfide group, C1-C4 ester group, C1-C4 alkyl group, halogenated C1-C4 alkyl group, C2-C4 alkenyl group, halogenated C2-C4 alkenyl group, C2-C4 alkynyl group, halogenated C2-C4 alkynyl group, C3-C6 cycloalkyl group, C1-C6 alkoxy group, C2-C6 alkenyloxy group, C2-C6 alkynyloxy group, C1-C6 alkylthio group, C2-C6 alkenylthio group, C2-C6 alkynylthio group, unsubstituted phenyl group, -CO-NH-(C1-C4 alkyl group); Preferably, R5 is a group selected from the following group: vinyl, styryl, ethynyl, phenylacetylenyl, benzocyclobutenyl, vinylbenzocyclobutenyl, trifluorovinyl phenyl ether, cyano, epoxy group, cyanate group, isocyanate group.

3. The modified polymer according to claim 1, wherein The modified polymer has a monomer structure selected from the following group:

4. A method for preparing the modified polymer according to claim 1, characterized in that, Comprising the following steps: In an inert solvent, under the action of a catalyst, a polymer represented by the following formula (II) is reacted with a silane compound / siloxane compound containing a crosslinkable group represented by formula (III) to obtain a modified polymer represented by formula (I); Wherein, n0 is 1 to 2000, and n0 and n3 satisfy n0:(n0 + n3)=(0.01 to 1):1; n4 is an integer from 0 to 12; Each R1 and R2 is independently selected from the following group: H, a substituted or unsubstituted group selected from the following group: C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkenyl group, C3-C6 cycloalkynyl group, C1-C6 alkoxy group, C2-C6 alkenyloxy group, C2-C6 alkynyloxy group, 3-7 membered cycloalkoxy group, C1-C6 alkylthio group, C2-C6 alkenylthio group, C2-C6 alkynylthio group, C1-C6 alkylamino group, C2-C6 alkenylamino group, C2-C6 alkynylamino group, C6-C10 aryl group, C6-C10 aryloxy group, 5-10 membered heteroaryl group having 1-3 heteroatoms each independently selected from N, O and S, benzo 5-6 membered heterocyclic group, benzo C3-6 cycloalkyl group, benzo C4-6 cycloalkenyl group, benzo C4-6 cycloalkynyl group, C1-C6 hydroxyalkyl group, C2-C6 hydroxyalkenyl group, C2-C6 hydroxyalkynyl group, hydroxyphenyl group, ureido group, amino ester group, isocyanate group (-N=C=O), cyanate group (-O-CN); R3, R4, and R5 are each independently selected from the following group: H, a substituted or unsubstituted group selected from the following: 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, 5-10 membered heteroaryl having 1-3 heteroatoms each independently selected from N, O, and S, benzo 5-6 membered heterocyclic group, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, C1-C6 hydroxyalkyl, C2-C6 hydroxyalkenyl, C2-C6 hydroxyalkynyl, hydroxyphenyl (-Ph-OH), ureido, aminoester group, -CO-NH-(C1-C4 alkyl), isocyanate group, cyanate group; The said substitution means that one or more hydrogens on the group are substituted by substituents selected from the following group: halogen, silyl (-SiR3), cyano, hydroxy, mercapto, amino, carboxyl, phenyl ether group, phenylthioether group, C1-C4 ester group, C1-C4 alkyl, halo C1-C4 alkyl, C2-C4 alkenyl, halo C2-C4 alkenyl, C2-C4 alkynyl, halo 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, benzo C3-6 cycloalkyl, benzo C4-6 cycloalkenyl, benzo C4-6 cycloalkynyl, -CO-NH-(C1-C4 alkyl); and phenyl having 1-3 substituents selected from the following group: halogen, cyano, hydroxy, mercapto, amino, carboxyl, C1-C4 alkyl, C2-C4 alkenyl, halo C2-C4 alkenyl, C2-C4 alkynyl, halo C2-C4 alkynyl, isocyanate group, cyanate group; Wherein, the monomer structure shown in Formula I contains m degrees of unsaturation, and m is 2-10; Alternatively, in the monomer structure represented by Formula I contains p crosslinkable groups or bonds, and p is 1-10, wherein, the said crosslinkable groups or bonds are selected from the following group: cyano (CN), hydroxy (-OH), mercapto (-SH), amino (-NH2), carboxyl (-COOH), urethane group (-O-C(O)-NH-), ureido (-NH-C(O)-NH-), ether bond (-O-), thioether bond (-S-), ester bond (-C(O)O-), alkenyl, alkynyl, phenyl, heterocyclic group, cycloalkenyl, cycloalkynyl, isocyanate group, cyanate group.

5. The method according to claim 4, characterized in that, The said method has the following characteristics: (a) The molar ratio of the polymer of Formula (II) and the silane compound containing crosslinkable groups shown in Formula (III) is 1:(0.01 - 2); preferably 1:(0.2 - 0.8), more preferably 1:(0.3 - 0.6); (b) The molar volume ratio of the silane compound containing a crosslinkable group represented by the formula (III) to the inert solvent is 0.05 - 0.5 mol / L, preferably 0.06 - 0.3 mol / L; and / or (c) The mass molar ratio of the catalyst to the silane compound containing a crosslinkable group represented by the formula (III) is 0.025–0.25 g / mol, preferably 0.05 - 0.2 g / mol; and / or (d) The reaction temperature is 30 - 160 °C; preferably 50 - 150 °C; more preferably 60 - 130 °C.

6. A silane compound / siloxane compound containing a crosslinkable group as described in formula (III), characterized in that, Wherein, R1, R2, R3, R4 and R5 are as described in claim 1.

7. A cured product, characterized in that, The cured product is obtained by crosslinking reaction of the curing raw materials, wherein the curing raw materials are the modified polymer described in claim 1, or a blend of the modified polymer described in claim 1 and other curable monomers or polymers.

8. A method for preparing the cured product according to claim 7, characterized in that, Comprising the following steps: Under the protection of an inert gas, the curing raw materials are heated and cured to obtain a cured product; wherein the curing raw materials are the modified polymer described in claim 1, or a blend of the modified polymer described in claim 1 and other thermally curable monomers or polymers.

9. An article, characterized in that, Prepared from the modified polymer described in claim 1 or the cured product described in claim 7, or comprising the modified polymer described in claim 1 or the cured product described in claim 7.

10. Use of the article according to claim 9, characterized in that, For preparing high-frequency low-dielectric constant materials, wherein the high-frequency low-dielectric constant materials are selected from the group consisting of: low-dielectric thin film substrate materials, low-dielectric thin films, low-dielectric constant matrix resins, low-dielectric encapsulation materials, low-dielectric constant photo-patterning materials.

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