CN106916312B - Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof - Google Patents

Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof Download PDF

Info

Publication number
CN106916312B
CN106916312B CN201710156298.9A CN201710156298A CN106916312B CN 106916312 B CN106916312 B CN 106916312B CN 201710156298 A CN201710156298 A CN 201710156298A CN 106916312 B CN106916312 B CN 106916312B
Authority
CN
China
Prior art keywords
solvent
monomer
magnesium
bromobenzocyclobutene
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710156298.9A
Other languages
Chinese (zh)
Other versions
CN106916312A (en
Inventor
李娴
杨军校
钟楠
范立
胡欢
黄亚文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest University of Science and Technology
Original Assignee
Southwest University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest University of Science and Technology filed Critical Southwest University of Science and Technology
Priority to CN201710156298.9A priority Critical patent/CN106916312B/en
Publication of CN106916312A publication Critical patent/CN106916312A/en
Application granted granted Critical
Publication of CN106916312B publication Critical patent/CN106916312B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a thermally crosslinkable hyperbranched polymer of formula (III)The preparation method of the hyperbranched polycarbosilane benzocyclobutene resin comprises the following steps: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium is 1: 1-10: 1-10: 1-2, taking the raw materials according to a molar ratio, taking iodine as an initiator and tetrahydrofuran or/and diethyl ether as a solvent, and diluting the raw materials to prepare a solution; putting magnesium and iodine particles into a reactor, stirring, and sequentially dropwise adding chloromethyl trichlorosilane, 4-bromobenzene benzocyclobutene and tetrahydrofuran or/and ether solution of halogenated alkane at the temperature of 30-80 ℃ for reaction; adding water into the reacted materials to stop the reaction, extracting by an organic solvent, drying, distilling and concentrating to remove the solvent, and then distilling or carrying out silica gel column chromatography to obtain the product. The resin has excellent thermal and electrical properties, and can be used in the fields of microelectronic industry, aerospace, national defense and the like.

Description

Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof
Technical Field
The invention belongs to an organic polymer compound and preparation thereof, and relates to a hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked and a preparation method thereof. The hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked has excellent thermal and electrical properties, and can be used as a high-performance dielectric film material or a packaging material in the fields of microelectronic industry, aerospace, national defense and the like.
Background
In the prior art, Polycarbosilane (PCS) is an organosilicon polymer formed by elements such as Si, C, and H, and the molecular chain is a linear or branched structure, and has excellent performances such as high temperature resistance (up to 400 ℃), low dielectric constant (as low as 2.5), moisture absorption resistance, and the like, and is an important silicon carbide ceramic precursor (precaramic polymers) and widely applied to the field of high-performance ceramics. The hyperbranched polycarbosilane is an important type of polycarbosilane, and has great importance in the preparation of ceramic materials due to simple preparation and cheap and easily-obtained raw materialsTo be applied, there have been many reports on the preparation of hyperbranched polycarbosilanes, such as: in US2007/0093587A1, US2007/0167599A1, CN102675649A, CN104177621A, [ Organometallics,1991,10(5),1336-]In the literature, the hyperbranched polycarbosilane is prepared by using chloromethyl trichlorosilane or partially methoxylated chloromethyl chlorosilane as a raw material. In these reports, the active functional groups Si-Cl or Si-OCH in the prepared hyperbranched polycarbosilane3The bond is chemically unstable and eventually converts to Si-CH3、Si-CH2CH3SiH or SiOH to facilitate the increase of its ceramization rate or other applications, but this also limits its application in a wider range. The hyperbranched polycarbosilane also has excellent performances such as high heat resistance, low dielectric, good film-forming performance and the like. This makes it potentially useful in a wide range of applications in the field of dielectric materials, such as in the literature: [ ACS Applied Materials&Interfaces,2012,4,2659-2663]Polycarbosilane is reported to have excellent film-forming properties and a low dielectric constant (2.5), but the application value of the polycarbosilane is limited because the polycarbosilane is used for synthesizing an intermediate of disilicon cyclobutane, the yield is low, the curing temperature is high, and the temperature is 300-400 ℃.
Benzocyclobutene resin has excellent performances such as heat resistance, dielectric property, moisture absorption resistance, film flatness and the like, and various benzocyclobutene organic silicon polymers and preparation methods thereof are reported in the invention patents or documents, for example: US5882836, US5138081, ZL201110367893.x, ZL201110367900.6 etc. report several polysiloxane type benzocyclobutene silicone resins; the literatures [ Journal of Polymer Science, Part A: Polymer Chemistry,2011,49, 381-.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked and a preparation method thereof. The hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat has the characteristics of highly branched crosslinkable units, good film forming property, low heat crosslinking temperature and the like, and can form a high-performance thermosetting film material or a casting molding material after crosslinking at about 230 ℃. The preparation method of the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked starts from cheap and easily-obtained chloromethyl trichlorosilane, firstly, the self Grignard (Grignard) coupling reaction is carried out, then 4-bromo benzocyclobutene and (or) halogenated alkane are added in situ, and the target polymer (namely the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked) is directly prepared by a one-pot method.
The invention discloses a hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat and a preparation method thereof, which mainly comprises the following steps: chloromethyl trichlorosilane produces Grignard reagent by itself under the action of magnesium, then the Grignard reagent and Si-Cl generate coupling reaction, and hyperbranched polycarbosilane polymer containing Si-Cl bonds is formed, after reaction for a period of time, a certain amount of 4-BrBCB is added into the reaction system, after reaction for a period of time, a certain amount of halogenated alkane is added into the system, after reaction for a period of time at a certain temperature, after cooling, a certain amount of distilled water (or deionized water) is added into the reaction system for quenching reaction, solvent extraction and concentration are carried out, and then purification steps such as distillation or silica gel column chromatography are carried out, so that the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked can be obtained.
The content of the invention is as follows: a hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat is characterized in that: the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked has a chemical structural formula shown in a formula (III):
Figure GDA0001364843000000031
in the formula (III):
Figure GDA0001364843000000032
the molecular weight of the hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked is 2000-20000;
the hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being crosslinked by heat is basically characterized in that: white or yellowish viscous jelly; the structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Another aspect of the invention is: a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat is characterized by comprising the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1: 1-10: 1-10: 1-2 molar ratio of the raw material chloromethyl trichlorosilane (Cl)3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB, or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X, or called monomer II), and catalyst magnesium (Mg) (scrap); taking iodine (particles) as an initiator (the mass of iodine is preferably 0.1-2% of that of magnesium);
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: taking a solvent according to a volume ratio of 5-30, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: taking a solvent according to a volume ratio of 5-30, and diluting 4-bromobenzocyclobutene with the solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: taking a solvent according to the volume ratio of 5-30, and diluting halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Putting magnesium (scraps) (preferably polished magnesium) and iodine granules into a reactor under protection, stirring, slowly dropwise adding the solution A, heating to the temperature of 30-80 ℃ after dropwise adding, wherein the optimal reaction temperature is related to the selected diluting solvent, and continuously reacting for 4-16 h (preferably 10-12 h) under stirring; then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 30-80 ℃ (the optimal reaction temperature is related to the selected diluting solvent) after dropwise adding is finished, and continuously reacting for 4-12 h (the better reaction time is 6-8 h); then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 30-80 ℃ (the optimal reaction temperature is related to the selected diluting solvent) after dropwise adding is finished, and continuously reacting for 4-12 h (the better reaction time is 6-8 h); the whole reaction process can better keep the (gentle) reflux of the reaction materials; obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove substances dissolved in water in the reacted materials, stopping the reaction on the basis of the principle that the added water is beneficial to separation and purification, and the volume of the added water is preferably 0.2-2 times of the volume of the reacted materials to obtain a mixed material; extracting with organic solvent (the organic solvent for extraction is any one of common organic solvents capable of separating with water, such as petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene and toluene, the dosage and frequency of the organic solvent for extraction are based on the principle that the product in the water phase can be completely extracted, the volume dosage of the organic solvent for each extraction is preferably 0.5-2 times of that of the mixed material), and drying the organic phase with inorganic salt desiccant (anhydrous CaCl, which is a desiccant commonly used in laboratories or factories)2Or anhydrous Na2SO4The amount of the drying agent is preferably 5-20% of the mass of the organic phase, the drying time is preferably 2-5 hours, and the drying agent can be left standing overnight), then the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and the concentrated material is distilled (can be distilled under normal pressure or reduced pressure; the temperature required by reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃ and the like) or silica gel column chromatography (the solvent used by column chromatography can be petroleum ether or normal hexane) to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked;
the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being crosslinked by heat has the following basic characteristics: white or yellowish viscous jelly; the structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
In another aspect of the invention: the preferable step a is:
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: taking a solvent according to a volume ratio of 10-20, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: taking a solvent according to a volume ratio of 15-20, and diluting 4-bromobenzocyclobutene with the solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane or halogenated olefin (R-X): the solvent is 1: taking a solvent according to a volume ratio of 15-20, and diluting halogenated alkane or halogenated olefin with the solvent to prepare a solution of a monomer II.
In another aspect of the invention: the ingredients in the step a are preferably as follows: by chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1:4:4:1.5 molar ratio of chloromethyl trichlorosilane (Cl) as a raw material3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB, or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X, or called monomer II), and catalyst magnesium (Mg) (scrap).
In another aspect of the invention: the chemical structural formula of the used 4-bromobenzocyclobutene (4-BrBCB) is shown as (I), and the chemical structural formula of the used haloalkane is shown as (II):
R-X
R＝CnH2n+1，n＝1，2，3，4，6，8，10，16，18；X＝Cl、Br、l
(II)
compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the invention adopts a one-pot method for synthesis, and each reactant is added in batches in sequence without purification and separation links in the middle; the preparation is simple, the process is simple and convenient, the operation is easy, and the practicability is strong;
(2) excellent thermal stability: according to the invention, polycarbosilane is used as a main skeleton, and the bond with high carbon-silicon bond can enable the polycarbosilane (namely, the hyperbranched polycarbosilane benzocyclobutene resin which can be photo-thermally double-crosslinked) to have good thermal stability through crosslinking;
(3) low dielectric constant and dielectric loss: the polymer does not introduce high-polarity chemical bonds, and takes the carbon-carbon bond and the carbon-silicon bond with low dipole moment as frameworks, so that the low dielectric constant (2.4-2.6) and the low dielectric loss (0.005) of the polymer are ensured, and the resin is also particularly suitable for the field of high-frequency transmission due to the structural characteristics of the polymer;
(4) good film-forming properties and film flatness: the resin prepared by the invention is colorless or faint yellow sticky jelly, has good molding processability, does not release small molecular substances during curing, and ensures that the film does not generate defects such as air bubbles, pinholes and the like, thereby having excellent film-forming property;
(5) good mechanical properties and can be adjusted as required: the invention can adjust the mechanical property by adjusting the proportion of the introduced crosslinkable units, and can well control the proportion of the 'rigid' chain segment and the 'flexible' chain segment of the polymer by controlling the crosslinking degree of the polymer.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and chloromethyl trichlorosilane, monomer I, monomer II and magnesium (Mg) are fed according to the molar ratio of 1:2:2: 1.5.
Magnesium (Mg) (0.36g,15mmol) and a catalytic amount of iodine were added to a dry flask equipped with a magnetic stirrer, a constant pressure dropping funnel, and a reflux condenser, sealed, evacuated, and charged with nitrogen to remove oxygen in the system, and repeated three times. Under the protection of nitrogen, chloromethyl trichlorosilane (Cl) is added into a constant-pressure dropping funnel3SiCH2Cl) (1.84g,10mmol) in Tetrahydrofuran (THF) (37.5mL) solution, a little bit of the solution is added into the flask to initiate the reaction by slight heating, after the reaction is initiated, the mixed solution is slowly added into the flask from a constant pressure dropping funnel by dropwise adding, the mixture is stirred, the temperature is increased to 65 ℃ after the dropwise adding, the stirring is continued, and the reaction is continued for 10 hours, thus obtaining an intermediate 1. A solution of 4-bromobenzocyclobutene (4-BrBCB) (3.66g,20mmol) in Tetrahydrofuran (THF) (49.8mL) was added to the flask, slowly added dropwise to the flask, stirred at 65 ℃ and reacted continuously for 5 h. Adding bromooctane (C)8H17Br) (3.86g,20mmol) in Tetrahydrofuran (THF) (69.7mL) was poured into a constant pressure dropping funnel and slowly droppedThe mixture was added to a flask, stirred at 65 ℃ and reacted continuously for 5 hours. The whole reaction process is kept under gentle reflux. After the reaction is finished, cooling to room temperature, and slowly dropwise adding a proper amount of distilled water to quench the reaction. Extracting with toluene, mixing organic phases, and extracting with anhydrous Na2SO4Drying, standing overnight, suction filtering, purifying with silica gel column, removing solvent by rotary evaporation, and drying in vacuum drying oven at room temperature for 20 hr to obtain viscous gel polymer, i.e. the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
The basic characteristics of the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked are as follows: white or yellowish viscous jelly. The structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Example 2:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and chloromethyl trichlorosilane, monomer I, monomer II and magnesium (Mg) are fed according to the molar ratio of 1:3:2: 1.5.
Magnesium (Mg) (0.36g,15mmol) and a catalytic amount of iodine were added to a dry flask equipped with a magnetic stirrer, a constant pressure dropping funnel, and a reflux condenser, sealed, evacuated, and charged with nitrogen to remove oxygen in the system, and repeated three times. Under the protection of nitrogen, chloromethyl trichlorosilane (Cl) is added into a constant-pressure dropping funnel3SiCH2Cl) (1.84g,10mmol) in Tetrahydrofuran (THF) (37.5mL) was added dropwise a little bit to the flask to initiate the reaction slightly thermally, after the reaction was initiated, the mixture was slowly added dropwise from a constant pressure dropping funnel, stirred,heating to 65 ℃ after dripping, continuing stirring, and continuously reacting for 10h to obtain an intermediate 1. A solution of 4-bromobenzocyclobutene (4-BrBCB) (5.49g,30mmol) in Tetrahydrofuran (THF) (74.7mL) was added to the flask, slowly added dropwise to the flask, stirred at 65 ℃ and reacted continuously for 5 h. Adding bromooctane (C)8H17Br) (3.86g,20mmol) in Tetrahydrofuran (THF) (69.7mL) was poured into a constant pressure dropping funnel, slowly dropped into the flask, stirred at 65 ℃ and reacted for 5h continuously. The whole reaction process is kept under gentle reflux. After the reaction is finished, cooling to room temperature, and slowly dropwise adding a proper amount of distilled water to quench the reaction. Extracting with toluene, mixing organic phases, and extracting with anhydrous Na2SO4Drying, standing overnight, suction filtering, purifying with silica gel column, removing solvent by rotary evaporation, and drying in vacuum drying oven at room temperature for 20 hr to obtain viscous gel polymer, i.e. the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
The basic characteristics of the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked are as follows: white or yellowish viscous jelly. The structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Example 3:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:2: 1.5.
The preparation method is the same as that of example 1 and is omitted.
The basic characteristics are as follows: white or yellowish viscous jelly; the structural characterization results were the same as in example 1.
Example 4:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:3: 1.5.
The preparation method is the same as example 1.
The basic characteristics are as follows: white or yellowish viscous jelly; the structural characterization results were the same as in example 1.
Example 5:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:4: 1.5.
The preparation method is the same as example 1.
The basic characteristics are as follows: white or yellowish viscous jelly; the structural characterization results were the same as in example 1.
Example 6:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:4: 1.5.
Hyperbranched polymerization: anhydrous oxygen-free nitrogen (N)2) In the atmosphere, magnesium chips (Mg) and diethyl ether (Et) are added2O) and chloromethyl trichlorosilane are taken according to the molar ratio of 1.5:20:1, and magnesium chips (Mg) are added into the second portIn a flask, chloro-methyl trichlorosilane (Cl)3SiCH2Cl) of diethyl ether (Et)2O) solution is added into a constant pressure dropping funnel, slowly dropped into a flask, and stirred for 8 hours at the reaction temperature of 30-45 ℃. The whole reaction process is kept under gentle reflux.
Grafting: grafting monomer I, diethyl ether (Et)2O) is mixed liquid which is 4 times and 15 times of the molar weight of the polymerization monomer, added into the product, and continuously heated and stirred (30-45 ℃) to react for about 6 hours. Grafting monomer II, diethyl ether (Et)2O) is mixed liquid which is 4 times and 15 times of the molar weight of the polymerization monomer, and the mixture is added into the product, and the mixture is continuously heated and stirred (30-45 ℃) for about 6 hours. The reaction is stopped, cooled to room temperature, and quenched by slowly dropping a proper amount of distilled water. Extracting with petroleum ether, mixing organic phases, and adding anhydrous Na2SO4Drying, standing overnight, performing suction filtration, purifying by using a silica gel column, removing a solvent by rotary evaporation, and drying in a vacuum drying oven at room temperature for 10-20 hours to obtain viscous colloidal liquid, namely a hyperbranched graft copolymer target product, namely the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
Example 7:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:3: 1.5.
The procedure for hyperbranched polymerization and grafting was the same as in example 6.
Example 8:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:3:3: 1.3.
The procedure for hyperbranched polymerization and grafting was the same as in example 6.
Example 9:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: 2-b4 preparation: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:2:4: 1.3.
The procedure of hyperbranched polymerization and grafting was the same as in example 6.
Example 10:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctane (C)8H17Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:2: 1.5.
The procedure of hyperbranched polymerization and grafting was the same as in example 6.
Example 11:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:4: 1.5.
Magnesium (Mg) (0.36g,15mmol) and a catalytic amount of iodine were added to a dry flask equipped with a magnetic stirrer, a constant pressure dropping funnel, and a reflux condenser, sealed, evacuated, and charged with nitrogen to remove oxygen in the system, and repeated three times. Under the protection of nitrogen, chloromethyl trichlorosilane (Cl) is added into a constant-pressure dropping funnel3SiCH2Cl) (1.84g,10mmol)And (3) dripping a Tetrahydrofuran (THF) (37.5mL) solution, slightly heating in a flask to initiate reaction, slowly dripping the mixed solution from a constant-pressure dropping funnel after the reaction is initiated, stirring, heating to 65 ℃ after dripping, continuously stirring, and continuously reacting for 10 hours to obtain an intermediate 1. A solution of 4-bromobenzocyclobutene (4-BrBCB) (7.32g,40mmol) in Tetrahydrofuran (THF) (74.7mL) was added to the flask, which was slowly added dropwise to the flask, stirred at 65 ℃ and reacted continuously for 5 h. Bromoethane (C) will be added2H5Br) (4.36g,40mmol) in Tetrahydrofuran (THF) (44.8mL) was poured into a constant pressure dropping funnel, slowly dropped into the flask, stirred at 65 ℃ and reacted for 5h continuously. The whole reaction process is kept under gentle reflux. After the reaction is finished, cooling to room temperature, and slowly dropwise adding a proper amount of distilled water to quench the reaction. Extracting with toluene, mixing organic phases, and extracting with anhydrous Na2SO4Drying, standing overnight, performing suction filtration, purifying by using a silica gel column, removing the solvent by rotary evaporation, and drying in a vacuum drying oven at room temperature for 10-20 h to obtain a viscous colloidal polymer, namely the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
The basic characteristics are as follows: white or yellowish viscous jelly; the structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Example 12:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:3: 1.5.
The preparation method is the same as example 11.
The basic characteristics are as follows: white or yellowish viscous jelly; the results of structural characterization were the same as in example 11.
Example 13:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) solution as solvent, and using chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:2: 1.5.
The preparation method is the same as example 11.
The basic characteristics are as follows: white or yellowish viscous jelly; the results of structural characterization were the same as in example 11.
Example 14:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:3:4: 1.5.
The preparation method is the same as example 11.
The basic characteristics are as follows: white or yellowish viscous jelly; the results of structural characterization were the same as in example 11.
Example 15:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:4: 1.5.
Hyperbranched polymerization: anhydrous oxygen-free nitrogen (N)2) In the atmosphere, adding magnesium chips (Mg) and diethyl ether(Et2O) and chloromethyl trichlorosilane are taken according to the molar ratio of 1.5:20:1, magnesium chips (Mg) are added into a two-neck flask, and chloromethyl trichlorosilane (Cl) is contained3SiCH2Cl) of diethyl ether (Et)2O) solution is added into a constant pressure dropping funnel, slowly dropped into a flask, and stirred for 8 hours at the reaction temperature of 30-45 ℃. The whole reaction process is kept under gentle reflux.
Grafting: grafting monomer I, diethyl ether (Et)2O) is mixed liquid which is 4 times and 15 times of the molar weight of the polymerization monomer, added into the product, and continuously heated and stirred (30-45 ℃) to react for about 6 hours. Grafting monomer II, diethyl ether (Et)2O) is mixed liquid which is 4 times and 15 times of the molar weight of the polymerization monomer, and the mixture is added into the product, and the mixture is continuously heated and stirred (30-45 ℃) for about 6 hours. The reaction is stopped, cooled to room temperature, and quenched by slowly dropping a proper amount of distilled water. Extracting with petroleum ether, mixing organic phases, and adding anhydrous Na2SO4Drying, standing overnight, performing suction filtration, purifying by using a silica gel column, removing a solvent by rotary evaporation, and drying in a vacuum drying oven at room temperature for 10-20 hours to obtain viscous colloidal liquid, namely a hyperbranched graft copolymer target product, namely the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
Example 16:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:4: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 15.
Example 17:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) according to chloromethyl trichlorosilane monomerFeeding the monomer II and magnesium (Mg) in a molar ratio of 1:3:4: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 15.
Example 18:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:3:3: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 15.
Example 19:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), chlorobutane (C)4H9Cl), and feeding chloromethyl trichlorosilane, a monomer I, a monomer II and magnesium (Mg) according to a molar ratio of 1:4:4: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 1.
Example 20:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), chlorobutane (C)4H9Cl) is prepared, and chloromethyl trichlorosilane, a monomer I, a monomer II and magnesium (Mg) are fed according to the molar ratio of 1:3:2: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 20.
Example 21:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, ethyl ether (Et)2O) solution as solvent and chloromethyl trichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromoethane (C)2H5Br) according to chloromethyl trisCharging chlorosilane, monomer I, monomer II and magnesium (Mg) in a molar ratio of 1:4:4: 1.5. The procedure of hyperbranched polymerization and grafting was the same as in example 18.
Example 22:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctadecane (C)18H37Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:4:3: 1.3.
Hyperbranched polymerization: nitrogen (N)2) In the atmosphere, magnesium chips (Mg), Tetrahydrofuran (THF) and chloromethyl trichlorosilane are taken according to the molar ratio of 1.5:15:1, the magnesium chips (Mg) are added into a two-neck flask, and chloromethyl trichlorosilane (Cl) is contained3SiCH2Cl) was added to the constant pressure dropping funnel, slowly dropped into the flask, and stirred at a reaction temperature of 68 ℃ for 8 hours. The whole reaction process is kept under gentle reflux.
Grafting: adding grafting monomer I and Tetrahydrofuran (THF) into the product in an amount which is 4 times and 15 times of the molar weight of the polymerized monomers, continuously heating and stirring (68 deg.C is added into the product, continuously heating and stirring (68 deg.C) for about 5h, stopping the reaction, cooling to room temperature, slowly dropwise adding a proper amount of distilled water to quench the reaction, extracting with n-hexane, combining organic phases, and adding anhydrous Na2SO4Drying, standing overnight, suction filtering, purifying with silica gel column, removing solvent by rotary evaporation, and drying in a vacuum drying oven at room temperature for 20h to obtain viscous colloidal liquid which is the target product of the hyperbranched graft copolymer, namely the thermally crosslinked hyperbranched polycarbosilane benzocyclobutene resin.
Example 23:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps: using magnesium (Mg) as catalyst, Tetrahydrofuran (THF) as solvent, and chloromethyltrichlorosilane (Cl)3SiCH2Cl), 4-bromobenzocyclobutene (4-BrBCB), bromooctadecane (C)18H37Br) is prepared, and the chloromethyl trichlorosilane, the monomer I, the monomer II and the magnesium (Mg) are fed according to the molar ratio of 1:3:4: 1.3. The procedure of hyperbranched polymerization and grafting was the same as in example 22.
Example 24:
a thermally crosslinkable hyperbranched polycarbosilane benzocyclobutene resin having a chemical structural formula shown in formula (III):
Figure GDA0001364843000000161
in the formula (III):
the molecular weight of the hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked is 2000-20000;
the hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being crosslinked by heat is basically characterized in that: white or yellowish viscous jelly; the structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Example 25:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1: 1: 1: 1 molar ratio of raw material chloromethyl trichlorosilane (Cl)3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X or called monomerII), and catalyst magnesium (Mg) (turnings); taking iodine (particles) as an initiator (the mass of iodine is preferably 0.1 percent of that of magnesium);
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: 5, taking a solvent according to the volume ratio, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: 5, taking a solvent according to the volume ratio, and diluting 4-bromobenzocyclobutene by using the solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: 5, taking a solvent according to the volume ratio, and diluting the halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Adding magnesium (scrap) (preferably polished magnesium) and iodine granules into a reactor under protection, stirring, slowly adding the solution A dropwise, heating to 30 deg.C, and (continuously) reacting under stirring for 16 h; then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 30 ℃ after dropwise adding, and continuously reacting for 12 hours; then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 30 ℃ after dropwise adding, and continuously reacting for 12 hours; obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove water-soluble substances in the reacted materials, stopping the reaction on the basis of the principle that the added water is beneficial to separation and purification, and the volume of the added water is 0.2 times of the volume of the reacted materials to obtain mixed materials; extracting with organic solvent (the organic solvent for extraction is common organic solvent capable of separating with water, and can be any one of petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene, and toluene, the amount and frequency of the organic solvent for extraction are determined based on the principle that the product in water phase can be completely extracted, and the volume of the organic solvent for extraction is 0.5 times of that of the mixture material), and the organic phase is inorganic saltDrying with desiccant (anhydrous CaCl, commonly used in laboratory or factory)2Or anhydrous Na2SO4The amount of the drying agent is 5 percent of the mass of the organic phase, and the drying time is 5 hours), then the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and the concentrated material is distilled (can be atmospheric distillation or reduced pressure distillation; the temperature required by reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃ and the like) or silica gel column chromatography (the solvent used by column chromatography can be petroleum ether or normal hexane) to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked;
the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being crosslinked by heat has the following basic characteristics: white or yellowish viscous jelly; the structure is characterized as follows: infrared Spectrum IR (KBr coated, cm)-1)：3057，2961，2927，2859，1578，1455，1396，1255，1048；1H NMR(600MHz，CDCl3)δ：0.07-0.08(3H,-SiCH3)，0.9(3H,-CH3)，1.43(2H,-CH2-)，3.15(4H,-CH2-)，6.8-7.3(3H,-ArH)；13C NMR(150MHz,CDCl3)δ:146.12，143.01，136.74，128.81，124.90，123.22，29.37，28.10，13.25。
Example 26:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1: 10: 10: 2 molar ratio of raw material chloromethyl trichlorosilane (Cl)3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB, or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X, or called monomer II), and catalyst magnesium (Mg) (scrap); taking iodine (particles) as an initiator (the mass of iodine is better to be 2 percent of that of magnesium);
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: 30 volume percent of solvent, and using the solvent to dissolve chloromethyl trichloro siliconDiluting with alkane to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: 30, diluting 4-bromobenzocyclobutene with a solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: taking a solvent according to the volume ratio of 30, and diluting halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Adding magnesium (scrap) (preferably polished magnesium) and iodine granules into a reactor under protection, stirring, slowly adding the solution A dropwise, heating to 80 deg.C, and (continuously) reacting under stirring 4; then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 80 ℃ after dropwise adding, and continuously reacting for 4 hours; then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 80 ℃ after dropwise adding, and continuously reacting for 4 ℃; obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove water-soluble substances in the reacted materials, and stopping the reaction to obtain mixed materials, wherein the amount of the added water is 2 times of the volume of the reacted materials on the principle of facilitating separation and purification; extracting with organic solvent (the organic solvent for extraction is one of common water-separable organic solvents such as petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene, and toluene, the amount and frequency of the organic solvent for extraction are determined by extracting the product in water phase completely, the volume of the organic solvent for extraction is 2 times of that of the mixture), drying the organic phase with inorganic salt desiccant (the desiccant is common in laboratory or factory, and can be anhydrous CaCl)2Or anhydrous Na2SO4The dosage of the drying agent is 20 percent of the mass of the organic phase, and the drying time is 2 hours), the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and then the organic phase is driedDistilling the concentrated material (atmospheric distillation or reduced pressure distillation; the temperature required by the reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃, and the like) or performing silica gel column chromatography (the solvent used by the column chromatography can be petroleum ether or n-hexane) to obtain white or light yellow viscous jelly, namely the prepared heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin (III); otherwise, the same as example 25 is omitted.
Example 27:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1: 5.5: 5.5: 1.5 molar ratio of chloromethyl trichlorosilane (Cl) as a raw material3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB, or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X, or called monomer II), and catalyst magnesium (Mg) (scrap); taking iodine (particles) as an initiator (the mass of iodine is better to be 1 percent of that of magnesium);
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: 18, diluting chloromethyl trichlorosilane with a solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: 18, diluting 4-bromobenzocyclobutene with a solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: 18, diluting the halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Adding magnesium (scrap) (preferably polished magnesium) and iodine granules into a reactor under protection, stirring, slowly adding the solution A dropwise, heating to 55 deg.C, and (continuously) reacting under stirring for 10 hr;then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 55 ℃ after dropwise adding, and continuously reacting for 8 hours; then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 55 ℃ after dropwise adding, and continuously reacting for 8 hours; obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove substances dissolved in water in the reacted materials, stopping the reaction on the basis of the principle that the added water is beneficial to separation and purification, and the volume of the added water is 1.1 times of the volume of the reacted materials to obtain mixed materials; extracting with organic solvent (the organic solvent for extraction is one of common organic solvents capable of separating with water, such as petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene, and toluene, the amount and frequency of the organic solvent for extraction are determined based on the principle that the product in water phase can be completely extracted, the volume of the organic solvent for extraction is 1.2 times of that of the mixture), drying the organic phase with inorganic salt desiccant (anhydrous CaCl is a common desiccant in laboratory or factory), and drying the organic phase with inorganic salt desiccant2Or anhydrous Na2SO4The amount of the drying agent is 12 percent of the mass of the organic phase, and the drying time is 3.5 hours), then the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and the concentrated material is distilled (can be normal pressure distillation or reduced pressure distillation; the temperature required by reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃ and the like) or silica gel column chromatography (the solvent used by column chromatography can be petroleum ether or normal hexane) to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked; otherwise, the same as example 25 is omitted.
Example 28:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1:4:4:1.5 molar ratio of chloromethyl trichlorosilane (Cl) as a raw material3SiCH2Cl), (graft monomer) 4-bromobenzo ringButene (4-BrBCB or monomer I), (grafting monomer) halogenated alkane (R-X or monomer II), and catalyst magnesium (Mg) (scrap); taking iodine (particles) as an initiator (the mass of iodine is preferably 0.9 percent of that of magnesium);
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: 16, diluting chloromethyl trichlorosilane with a solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: 16, diluting 4-bromobenzocyclobutene with a solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: 16, diluting halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Adding magnesium (scrap) (preferably polished magnesium) and iodine granules into a reactor under protection, stirring, slowly adding the solution A dropwise, heating to 60 deg.C, and (continuously) reacting under stirring for 12 hr; then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 60 ℃ after dropwise adding, and continuously reacting for 8 hours; then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 60 ℃ after dropwise adding, and continuously reacting for 8 hours; obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove water-soluble substances in the reacted materials, and stopping the reaction to obtain mixed materials, wherein the amount of the added water is 1 time of the volume of the reacted materials on the principle of facilitating separation and purification; extracting with organic solvent (the organic solvent for extraction is common organic solvent capable of separating with water, and can be any one of petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene, and toluene, the amount and frequency of the organic solvent for extraction are determined based on the principle that the product in water phase can be completely extracted,the volume of the organic solvent used in each extraction is 1 time of that of the mixed material), and the organic phase is dried by an inorganic salt drying agent (which is a drying agent commonly used in laboratories or factories and can be anhydrous CaCl)2Or anhydrous Na2SO4The amount of the drying agent is 10 percent of the mass of the organic phase, and the drying time is 4 hours), then the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and the concentrated material is distilled (can be normal pressure distillation or reduced pressure distillation; the temperature required by reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃ and the like) or silica gel column chromatography (the solvent used by column chromatography can be petroleum ether or normal hexane) to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked; otherwise, the same as example 25 is omitted.
Examples 29 to 35:
a preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat comprises the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium (Mg) is 1: 1-10: 1-10: 1-2 molar ratio of the raw material chloromethyl trichlorosilane (Cl)3SiCH2Cl), (grafting monomer) 4-bromobenzocyclobutene (abbreviated as 4-BrBCB, or called monomer I), (grafting monomer) haloalkane (abbreviated as R-X, or called monomer II), and catalyst magnesium (Mg) (scrap); taking iodine (particles) as an initiator (the mass of iodine in examples 29-35 is 0.3%, 0.5%, 0.8%, 1.1%, 1.3%, 1.6%, 1.8%, and the like of magnesium respectively);
the specific molar ratio and the use amount of the raw materials of each component in each example are shown in the following table:
Figure GDA0001364843000000231
according to chloromethyl trichlorosilane (Cl)3SiCH2Cl): the solvent is 1: taking a solvent according to a volume ratio of 5-30, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the formula (grafting monomer) of 4-bromobenzocyclobutene (short for 4-BrBCB): the solvent is 1: taking a solvent according to a volume ratio of 5-30 (in examples 29-35, the volume ratios are 1: 7, 1: 10, 1: 16, 1: 20, 1: 23, 1: 25 and 1: 28 respectively), and diluting 4-bromobenzocyclobutene with the solvent to prepare a solution of a monomer I;
according to the formula (grafting monomer) halogenated alkane (short for R-X): the solvent is 1: taking a solvent according to a volume ratio of 5-30 (in examples 29-35, the volume ratios are 1: 7, 1: 10, 1: 16, 1: 20, 1: 23, 1: 25 and 1: 28 respectively), and diluting the halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is Tetrahydrofuran (THF) or/and diethyl ether (Et)2O), other solvents that are also known in the art as Grignard reagents;
b. mixing and reacting: in the absence of water and oxygen, nitrogen (N)2) Putting magnesium (scraps) (preferably polished magnesium) and iodine particles into a reactor under protection, stirring, slowly dropwise adding the solution A, heating to the temperature of 30-80 ℃ after dropwise adding, and (continuously) reacting for 4-16 h (preferably 10-12 h) under stirring; then (slowly) dropwise adding the solution of the monomer I, stirring at the temperature of 30-80 ℃ after dropwise adding, and continuously reacting for 4-12 h (preferably 6-8 h); then (slowly) dropwise adding the solution of the monomer II, stirring at the temperature of 30-80 ℃ after dropwise adding, and continuously reacting for 4-12 h (preferably 6-8 h); obtaining reacted materials;
c. separation and purification: adding water (which can be distilled water or deionized water) into the reacted materials, stirring to remove substances dissolved in water in the reacted materials, stopping the reaction according to the principle that the added water is beneficial to separation and purification, and the volume of the added water is 0.2-2 times of the volume of the reacted materials to obtain mixed materials; extracting with organic solvent (the organic solvent for extraction is any one of common organic solvents capable of being separated from water, such as petroleum ether, diethyl ether, n-hexane, cyclohexane, ethyl acetate, dichloromethane, chloroform, benzene and toluene, the dosage and frequency of the organic solvent for extraction are based on the principle that the product in the water phase can be completely extracted, the volume dosage of the organic solvent for each extraction is 0.5-2 times of that of the mixed material), and drying the organic phase with inorganic salt drying agent (the organic solvent is commonly used in laboratories or factories)The agent can be anhydrous CaCl2Or anhydrous Na2SO4The amount of the drying agent is 5-20% of the mass of the organic phase, the drying time is 2-5 hours, or the drying agent can be kept still overnight), then the drying agent is removed by suction filtration, the organic phase is distilled and concentrated to remove the solvent, and the concentrated material is distilled (can be distilled under normal pressure or reduced pressure; the temperature required by reduced pressure distillation is related to the vacuum degree, for example, when the vacuum degree is 5mmHg, the temperature is 60-62 ℃ and the like) or silica gel column chromatography (the solvent used by column chromatography can be petroleum ether or normal hexane) to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked; otherwise, the same as example 25 is omitted.
In the above embodiment: all the raw materials are commercially available products.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, concentration, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above embodiments are the same as the prior art.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.

Claims (4)

1. A hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat is characterized in that: the hyperbranched polycarbosilane benzocyclobutene resin capable of being thermally crosslinked has a chemical structural formula shown in a formula (III):
Figure FDA0002274201530000011
in the formula (III):
Figure FDA0002274201530000012
CnH2n+1wherein n is 1, 2, 3, 4, 6, 8, 10, 16, 18
The molecular weight of the hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked is 2000-20000.
2. A preparation method of hyperbranched polycarbosilane benzocyclobutene resin capable of being crosslinked by heat is characterized by comprising the following steps:
a. preparing materials: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium is 1: 1-10: 1-10: 1-2, taking raw materials of chloromethyl trichlorosilane, 4-bromobenzocyclobutene, halogenated alkane and catalyst magnesium according to a molar ratio; taking iodine as an initiator;
according to chloromethyl trichlorosilane: the solvent is 1: taking a solvent according to a volume ratio of 5-30, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the weight ratio of 4-bromobenzocyclobutene: the solvent is 1: taking a solvent according to a volume ratio of 5-30, and diluting 4-bromobenzocyclobutene with the solvent to prepare a solution of a monomer I;
according to the formula of halogenated alkane: the solvent is 1: taking a solvent according to the volume ratio of 5-30, and diluting halogenated alkane with the solvent to prepare a solution of a monomer II;
the solvent is tetrahydrofuran or/and diethyl ether;
b. mixing and reacting: putting magnesium and iodine granules into a reactor under the protection of anhydrous oxygen-free nitrogen, dropwise adding the solution A under stirring, heating to the temperature of 30-80 ℃ after dropwise adding, and reacting for 4-16 hours under stirring; dropwise adding the solution of the monomer I, stirring at the temperature of 30-80 ℃ after dropwise adding, and continuously reacting for 4-12 hours; dropwise adding the solution of the monomer II, stirring at the temperature of 30-80 ℃ after dropwise adding, and continuously reacting for 4-12 hours; obtaining reacted materials;
c. separation and purification: adding distilled water or deionized water into the reacted materials to stop the reaction to obtain mixed materials; extracting with organic solvent, drying the organic phase with inorganic salt desiccant, vacuum filtering to remove the desiccant, distilling and concentrating the organic phase to remove the solvent, distilling or silica gel column chromatography to obtain white or light yellow viscous jelly, namely the prepared hyperbranched polycarbosilane benzocyclobutene resin (III) capable of being thermally crosslinked.
3. A process for preparing a thermally crosslinkable hyperbranched polycarbosilane benzocyclobutene resin according to claim 2, which comprises: the step a is as follows:
according to chloromethyl trichlorosilane: the solvent is 1: taking a solvent according to a volume ratio of 10-20, and diluting chloromethyl trichlorosilane with the solvent to prepare a solution A;
according to the weight ratio of 4-bromobenzocyclobutene: the solvent is 1: taking a solvent according to a volume ratio of 15-20, and diluting 4-bromobenzocyclobutene with the solvent to prepare a solution of a monomer I;
according to the formula of halogenated alkane: the solvent is 1: and (3) taking a solvent according to a volume ratio of 15-20, and diluting the halogenated alkane with the solvent to prepare a solution of a monomer II.
4. A process for preparing a thermally crosslinkable hyperbranched polycarbosilane benzocyclobutene resin according to claim 2 or 3, which comprises: the ingredients in the step a are: according to chloromethyl trichlorosilane: 4-bromobenzocyclobutene: halogenated alkanes: magnesium is 1:4:4:1.5 molar ratio of raw materials of chloromethyl trichlorosilane, 4-bromobenzocyclobutene, halogenated alkane and catalyst magnesium.
CN201710156298.9A 2017-03-16 2017-03-16 Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof Active CN106916312B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710156298.9A CN106916312B (en) 2017-03-16 2017-03-16 Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710156298.9A CN106916312B (en) 2017-03-16 2017-03-16 Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106916312A CN106916312A (en) 2017-07-04
CN106916312B true CN106916312B (en) 2020-02-07

Family

ID=59460504

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710156298.9A Active CN106916312B (en) 2017-03-16 2017-03-16 Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106916312B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197842B1 (en) * 1996-06-27 2001-03-06 Essilor International Compagnie Generale D'optique Material based on crosslinked silicone polymer comprising an attached photoinitiator, process for the preparation thereof, hydrophilic polymeric product obtained from this material and process for the preparation thereof, and novel photoinitiators
CN101265270A (en) * 2008-04-11 2008-09-17 西南科技大学 4-(1',1'-dimethyl-1'-vinyl)siliconbenzocyclobutene and preparation method thereof
CN102206229A (en) * 2011-04-14 2011-10-05 西南科技大学 Silicon-containing benzocyclobutene monomers and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197842B1 (en) * 1996-06-27 2001-03-06 Essilor International Compagnie Generale D'optique Material based on crosslinked silicone polymer comprising an attached photoinitiator, process for the preparation thereof, hydrophilic polymeric product obtained from this material and process for the preparation thereof, and novel photoinitiators
CN101265270A (en) * 2008-04-11 2008-09-17 西南科技大学 4-(1',1'-dimethyl-1'-vinyl)siliconbenzocyclobutene and preparation method thereof
CN102206229A (en) * 2011-04-14 2011-10-05 西南科技大学 Silicon-containing benzocyclobutene monomers and preparation method thereof

Also Published As

Publication number Publication date
CN106916312A (en) 2017-07-04

Similar Documents

Publication Publication Date Title
CN106957433B (en) Photo/thermal double-crosslinking hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof
US5484867A (en) Process for preparation of polyhedral oligomeric silsesquioxanes and systhesis of polymers containing polyhedral oligomeric silsesqioxane group segments
Wei et al. A fast convenient method to prepare hybrid sol-gel materials with low volume-shrinkages
JP2002212294A (en) Multibranched polycarbosilane, polycarbosiloxane, polycarbosilazene and copolymer thereof
WO1982003862A1 (en) Soluble polysilastyrene and method for preparation
CN1884343A (en) Novel carborane- (siloxane or silane)- ethinyl high temperature resistant polymer and its preparation method
WO2022105249A1 (en) Methods for preparing silsesquioxane containing silicon-hydrogen bonds and corresponding polymer thereof
CN110204730A (en) A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof
JP2010516881A (en) Method for producing organopolysiloxane
CN105837617B (en) Can directly heat cure the ether containing trifluoro vinyl cyclosiloxane preparation and application
JPH11255898A (en) Continuous preparation of polyorganosiloxane
KR100968803B1 (en) Polycarbosilane and method of producing it
US2684379A (en) Process for producing polysiloxanes
JP2023109867A (en) Silanol composition, cured product, adhesive, and method for curing silanol composition
CN106916312B (en) Heat-crosslinkable hyperbranched polycarbosilane benzocyclobutene resin and preparation method thereof
CN1709928A (en) Aryne resin containing silicone
AU606177B2 (en) New polycarbosilane useful for the manufacture of ceramic products and articles based on silicon carbide
CN108002377B (en) Preparation method of organosilane oligomer modified graphene
CN107057070B (en) Side-chain hydrogen-containing alkyne hybrid high-temperature-resistant polymer and preparation method thereof
JPH01131247A (en) Production of organopolysiloxane containing alkenyl group at end
KR20200078394A (en) Manufacturing method for Photocurable Polycarbosilane
CN101381463B (en) Polymer with backbone chain having silicon-aromatic bispropargyl ether structure and preparation method thereof
CN113087907A (en) Lithium silanol and preparation method and application thereof
CN110423350A (en) A kind of high-fire resistance silicon substrate benzyne resin of low-temperature setting and its preparation method and application
KR102481522B1 (en) Carbosilane Photocurable Composition and Manufacturing method of the Same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant