CN107417870A - A kind of organosilicon benzoxazine resin prepolymer based on eugenol and its preparation method and application - Google Patents

A kind of organosilicon benzoxazine resin prepolymer based on eugenol and its preparation method and application Download PDF

Info

Publication number
CN107417870A
CN107417870A CN201710257910.1A CN201710257910A CN107417870A CN 107417870 A CN107417870 A CN 107417870A CN 201710257910 A CN201710257910 A CN 201710257910A CN 107417870 A CN107417870 A CN 107417870A
Authority
CN
China
Prior art keywords
eugenol
organosilicon
benzoxazine resin
resin prepolymer
preparation
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.)
Granted
Application number
CN201710257910.1A
Other languages
Chinese (zh)
Other versions
CN107417870B (en
Inventor
代金月
刘小青
马松琪
腾娜
沈潇斌
江艳华
朱锦
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.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
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 Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201710257910.1A priority Critical patent/CN107417870B/en
Publication of CN107417870A publication Critical patent/CN107417870A/en
Application granted granted Critical
Publication of CN107417870B publication Critical patent/CN107417870B/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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention provides a kind of organosilicon benzoxazine resin prepolymer based on eugenol, its preparation method includes：(1) organic silicon monomer of eugenol and more hydrogen-baseds end-blocking is occurred hydrosilylation, obtains eugenol organo-silicon compound under catalyst action；(2) eugenol organo-silicon compound, diamines and paraformaldehyde are blended, under heating under the conditions of polymerisation occurs, the organosilicon benzoxazine resin prepolymer based on eugenol is prepared.Prepare simply, it is easy to operate, it is controllable to make, it is easy to implement, suitable for large-scale industrial production.Polymer prepared by organosilicon benzoxazine resin prepolymer of the present invention based on eugenol possesses good corrosion resistance, mechanical property and thermal property, the possibility with the existing petroleum-based products of replacement, and use range is extensive.

Description

A kind of organosilicon benzoxazine resin prepolymer based on eugenol and preparation method thereof And application
Technical field
The invention belongs to biological based thermoset applications, more particularly to a kind of organosilicon benzoxazine resin based on eugenol Prepolymer and its preparation method and application.
Background technology
Flourishing due to petroleum chemical industry in the last hundred years so that the application of petrochemicals is increasingly extensive.By It is greatly convenient that the various products and its derivative that oil obtains are brought to the life and production of people, has promoted the hair of society Exhibition and the progress of human civilization, but the various environmental problems at the same time brought equally can not look down upon.At the same time, oil provides Source is a kind of unsustainable, non-renewable resource, along with the increasingly depleted of its reserves, will necessarily cause to come from the height of oil The continuous improvement of molecular material cost.Recently, in the multiple pressure of environmental protection, reduction production cost with saving petroleum resources Under, utilized using the research and development that environment-friendly, sustainable resource is the bio-based high polymer material of raw material increasingly by section Grind the attention of boundary and industrial quarters.
Bio-based high polymer material is using sustainable resource as its main production raw material so that manufacture Polymer Industry reduces Dependence and consumption to petrochemical materials, while decrease dirt of the high polymer material to environment in preparation process is produced Dye, therefore bio-based high polymer material has environmental protection and saves the double effects of petroleum resources, is current high polymer material An important development direction, eugenol is a kind of naturally containing the nontoxic bio-based source compound of phenyl ring, widely should be had Use prospect.
Chinese patent literature such as the A of Publication No. CN 105503674 discloses a kind of polyfunctional group based on eugenol Unsaturated monomer, preparation method and applications, the invention provide the polyfunctional group unsaturated monomer structure based on eugenol in More active function groups can be introduced, are favorably improved the degree of cross linking of polymer, improve the glass transition temperature and heat of polymer Deformation temperature；The eugenol skeleton contained in monomer structure assigns the good mechanical property of polymer and thermal property, great Liang Rou Property key is favorably improved the performances such as the intensity of polymer, modulus, creep resistant, pliability.
Eugenol can be obtained by the organosilicon benzoxazine resin based on eugenol by Si―H addition reaction and polycondensation reaction Prepolymer.Mass produced using existing chemical industry equipment can, there is the advantages of yield is high, and technique is simple.Based on cloves Polymer prepared by the organosilicon benzoxazine resin prepolymer of phenol is enabled with its excellent performance such as heat-resisting, ageing-resistant It is used widely in the fields such as building, electronics, Aero-Space.Up to the present, it yet there are no in the prior art and pass through Si―H addition reaction The document and patent report of cloves phenolic group organosilicon benzoxazine resin prepolymer are prepared using eugenol with polycondensation reaction.Due to Eugenol derives from biomass material, and therefore, the exploitation of the organosilicon benzoxazine resin prepolymer based on eugenol can push away The development of dynamic bio-based materials, the sustainable development to fields such as the whole high polymer materials of promotion are significant.
The content of the invention
It is an object of the invention to solve above-mentioned technical problem present in prior art, there is provided a kind of based on eugenol Organosilicon benzoxazine resin prepolymer and its preparation method and application, bio-based source compound eugenol is used as raw material, The organosilicon benzoxazine resin prepolymer based on eugenol is obtained by Si―H addition reaction and polycondensation reaction, prepares simple, operation Simplicity, it is controllable to make, it is easy to implement, suitable for large-scale industrial production.
To solve above-mentioned technical barrier, the present invention uses following technical scheme：
A kind of organosilicon benzoxazine resin prepolymer based on eugenol, it is characterised in that have as shown in formula (I) Structure：
In formula (I), n is integer, R1Selected from the substituent as shown in formula (1)~(7),
R2Selected from C2H4、C3H6、C4H8、C5H10、C6H4、C6H12、C7H14And C8H16At least one of.
The organosilicon benzoxazine resin prepolymer has relative to traditional benzoxazine monomer in performance substantially to be carried The improvement of height, especially toughness, a kind of toughener can be used as.Due to R in structure1Difference, the organosilicon benzoxazine tree The toughness of fat prepolymer also has very big difference, and the more structure of siloxanes, the toughness that material is showed is stronger, corresponding mechanics Performance has certain decline.Preferably, R1During selected from substituent as shown in formula (1), (2), (3) or (4), material performance Go out very excellent toughness.
In addition, R in the organosilicon benzoxazine resin prepolymer structure2Difference, the toughness that material is showed also can Difference, R2Middle fatty chain length is longer, and the toughness that material is showed is stronger, and corresponding mechanical property has certain decline.
The organosilicon benzoxazine resin prepolymer based on eugenol of the present invention, directly use the cloves of bio-based source Phenol is prepared as raw material, it is possible to reduce dependence of the existing petroleum base benzoxazine resin to fossil resources and its dirt to environment Dye, it is a kind of bio-based, green, environment-friendly products, there are the double effects for saving petroleum resources and environmental protection.
The preparation method of the organosilicon benzoxazine resin prepolymer based on eugenol, including：
(1) organic silicon monomer of eugenol and more hydrogen-baseds end-blocking is occurred hydrosilylation, obtained under catalyst action To eugenol organo-silicon compound of the structure as shown in formula (II)；
In formula (II), R1Selected from the substituent as shown in formula (1)~(7),
(2) eugenol organo-silicon compound, diamines and paraformaldehyde are blended, under heating under the conditions of that polymerization occurs is anti- Should, the organosilicon benzoxazine resin prepolymer based on eugenol is prepared.
The organic silicon monomer of more hydrogen-based end-blockings is 1,1,3,3- tetramethyl disiloxanes, 1,3,5,7- tetramethyl tetrahydrochysenes Cyclotetrasiloxane, 1,1,3,3,5,5- hexam ethylcyclotrisiloxanes, 1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxanes, 1,1,3,3, The siloxanes of 5,5,7,7,9,9- decamethyls five, diphenyl silane, 1,1,3,3- tetra isopropyl disiloxanes or 1,1,5,5- tetramethyls Base -3,3- diphenyl trisiloxanes.
In step (1), the catalyst is Pt series catalysts, such as Karstedt catalyst, Speier catalyst.
In step (1), the mol ratio of the eugenol and the organic silicon monomer of more hydrogen-baseds end-blocking is 1~20：1.
In step (1), the dosage of catalyst is the 0.1~10% of the amount of eugenol material.
In step (1), the temperature of the hydrosilylation is 10~120 DEG C, and the reaction time is 0.5~72h.
The solvent of the polymerisation is any one in dioxane, toluene and its arbitrary proportion mixture, and dosage is 1~20 times of eugenol organosilicon compound amount of substance.
At the temperature and rate of charge, the product yield of hydrosilylation is higher.
Described diamines is ethylenediamine, propane diamine, butanediamine, pentanediamine, phenylenediamine, hexamethylene diamine, heptamethylene diamine and octamethylenediamine At least one of.
In step (2), the mol ratio of the eugenol organo-silicon compound, diamines and paraformaldehyde is 1：1~1.2：4~ 6。
In step (2), the temperature of the polymerisation is 0~120 DEG C, 0.5~70h of reaction time.
The solvent of the polymerisation is any one in dioxane, toluene and its arbitrary proportion mixture, and dosage is 1~20 times of eugenol organosilicon compound amount of substance.
Present invention also offers a kind of above-mentioned organosilicon benzoxazine resin prepolymer based on eugenol in high temperature bonding Application in agent.
The eugenol of biological source contains and petroleum-based compounds identical benzene ring structure in the present invention so that described in use Polymer prepared by the organosilicon benzoxazine resin prepolymer based on eugenol possesses good corrosion resistance, mechanical property Energy and thermal property, it is extensive with the possibility for substituting existing petroleum-based products, use range.
The present invention based on eugenol organosilicon benzoxazine resin prepolymer, prepare it is simple, it is easy to operate, can control It is good, it is easy to implement, suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 is the proton nmr spectra of double eugenol -1,1,3,3- tetramethyl disiloxanes prepared by embodiment 11H- NMR；
Fig. 2 is that double eugenol -1,1,3,3- tetramethyl disiloxanes-ethylenediamine organosilicon benzo prepared by embodiment 1 is disliked The proton nmr spectra of piperazine prepolymer1H-NMR；
Fig. 3 is that the nuclear-magnetism of double eugenol -1,1,5,5- tetramethyls -3,3- diphenyl trisiloxanes prepared by embodiment 2 is total to The hydrogen that shakes is composed1H-NMR；
Fig. 4 is that double eugenol -1,1,5,5- tetramethyl -3,3- diphenyl trisiloxanes-ethylenediamines prepared by embodiment 2 have The proton nmr spectra of machine silicon benzoxazine prepolymer1H-NMR。
Embodiment
With reference to embodiment, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention without For limiting the scope of the present invention.
In embodiment, proton nmr spectra1H-NMR is divided using the types of 400AVANCE III of Brooker company (Bruker) Instrument (Spectrometer) determines, 400MHz, deuterochloroform (CDCl3)。
The yield of eugenol organo-silicon compound is calculated by below equation：
The quality of yield=eugenol organo-silicon compound/(molal quantity of eugenol × eugenol organo-silicon compound Molal weight) × 100%；
The yield of organosilicon benzoxazine prepolymer based on eugenol is calculated by below equation：
The quality of yield=organosilicon benzoxazine prepolymer based on eugenol/(eugenol organo-silicon compound rub The molal weight of your number × organosilicon benzoxazine prepolymer based on eugenol) × 100%.
Embodiment 1
(1) 0.5mol eugenols, 0.2mol 1,1,3,3- tetramethyl disiloxanes, 0.01mol Karstedt are catalyzed Agent, it is dissolved in the mixed solution of 500mL dioxane and toluene, is reacted 32 hours at 70 DEG C, decompression rotary evaporation removes Mixed solvent, wash and double eugenols -1,1 are obtained after drying, 3,3- tetramethyl disiloxanes, shown in its structure such as formula (1-1), Yield is 95.5%, proton nmr spectra1H-NMR is as shown in figure 1, each peak on figure and double eugenols -1,1,3,3- tetramethyls The hydrogen atom of base disiloxane compound structure is all one-to-one.
(2) double eugenol -1,1,3,3- tetramethyl disiloxane compounds of the above-mentioned preparations of 0.1mol are dissolved in 180mL first 0.11mol ethylenediamines and 0.6mol paraformaldehydes are added after benzole soln, 0 DEG C is reacted 66 hours, is evaporated under reduced pressure and is removed mixed solvent, It is dried to obtain double eugenols -1,1,3,3- tetramethyl disiloxanes-ethylenediamine organosilicon benzoxazine prepolymer, its structure such as formula (1-2) is shown, i.e. the described organosilicon benzoxazine resin prepolymer based on eugenol, yield 91%.Hydrogen nuclear magnetic resonance Spectrum1HNMR is as shown in Fig. 2 each peak on figure and double eugenols -1,1,3,3- tetramethyl disiloxanes-ethylenediamine organosilicon benzene And the hydrogen atom above oxazines prepolymer structure is all one-to-one.
Double eugenol -1,1,3,3- tetramethyl disiloxanes-ethylenediamine organosilicon benzoxazine prepolymer is dried in air blast Case carries out being heated to 120 DEG C of solidifications, obtains based on double eugenols -1,1,3,3- tetramethyl disiloxanes-ethylenediamine organosilicon benzene And the cured product of oxazines.The stretch modulus of the cured product of gained is 2935MPa, elongation at break 6.0%, tensile strength For 91MPa, Td10For 420 DEG C.
Embodiment 2
(1) by 0.5mol eugenols, 0.15mol 1,1,5,5- tetramethyl -3,3- diphenyl trisiloxanes, 0.02mol Speier catalyst, it is dissolved in the mixed solution of 500mL dioxane and toluene, is reacted 22 hours at 30 DEG C, decompression rotation Turn evaporative removal mixed solvent, wash and double eugenols -1,1, the silica of 5,5- tetramethyl -3,3- diphenyl three are obtained after drying Alkane, shown in its structure such as formula (1-3), yield 97.1%, proton nmr spectra1H-NMR is as shown in figure 3, each peak on figure All it is with the hydrogen atom above double eugenol -1,1,5,5- tetramethyls -3,3- diphenyl trisiloxanes compound structures one a pair Answer.
(2) by double eugenol -1,1,5,5- tetramethyls -3,3- diphenyl trisiloxanes compounds of the above-mentioned preparations of 0.1mol 0.11mol ethylenediamines and 0.57mol paraformaldehydes are added after being dissolved in the mixed solution of 210mL dioxane and toluene, 15 DEG C anti- Answer 18 hours, be evaporated under reduced pressure and remove mixed solvent, be dried to obtain double eugenols -1,1, the silicon of 5,5- tetramethyl -3,3- diphenyl three Oxygen alkane-ethylenediamine organosilicon benzoxazine prepolymer, the i.e. described organosilicon benzoxazine resin prepolymer based on eugenol, Shown in its structure such as formula (1-4), yield 93%.Proton nmr spectra1H NMR are as shown in figure 4, each peak on figure and double fourths Hydrogen above fragrant phenol -1,1,5,5- tetramethyl -3,3- diphenyl trisiloxanes-ethylenediamine organosilicon benzoxazine prepolymer structure Atom is all one-to-one.
By double eugenol -1,1,5,5- tetramethyl -3,3- diphenyl trisiloxanes-ethylenediamine organosilicon benzoxazine pre-polymerization Thing, UV solidifications are carried out with 500W box uv cure machine, obtained based on double eugenols -1,1,5,5- tetramethyls -3,3- bis- The cured product of phenyl trisiloxanes-ethylenediamine organosilicon benzoxazine prepolymer.The stretch modulus of the solidfied material of gained is 3935MPa, elongation at break 4.0%, tensile strength 120MPa, Td10For 430 DEG C.
Embodiment 3
(1) 0.5mol eugenols, 0.17mol 1,1,3,3- tetra isopropyl disiloxanes, 0.01molSpeier are catalyzed Agent, it is dissolved in the mixed solution of 500mL dioxane and toluene, is reacted 31 hours at 40 DEG C, decompression rotary evaporation removes Mixed solvent, wash and double eugenols -1,1,3,3- tetra isopropyl disiloxane compounds, yield 89% are obtained after drying.
(2) double eugenol -1,1,3,3- tetra isopropyl disiloxane compounds of the above-mentioned preparations of 0.1mol are dissolved in 250mL 0.1mol propane diamine and 0.53mol paraformaldehydes are added after dioxane solution, 30 DEG C are reacted 26 hours, are evaporated under reduced pressure to remove and are mixed Bonding solvent, is dried to obtain double eugenols -1,1,3,3- tetra isopropyl disiloxanes-propane diamine organosilicon benzoxazine prepolymer, Shown in its structure such as formula (1-5), yield 98%.
By double eugenols -1,1,3,3- tetra isopropyl disiloxanes-propane diamine organosilicon benzoxazine prepolymer, 500W is used Box uv cure machine carry out UV solidifications, obtain based on double eugenols -1,1,3,3- tetra isopropyl disiloxanes-propane diamine The cured product of organosilicon benzoxazine prepolymer.The stretch modulus of the solidfied material of gained is 2035MPa, and elongation at break is 7.0%, tensile strength 70MPa, Td10For 423 DEG C.
Embodiment 4
(1) 0.5mol eugenols, 0.1mol 1,1,3,3- tetra isopropyl disiloxanes, 0.04molSpeier are catalyzed Agent, it is dissolved in the mixed solution of 500mL dioxane and toluene, is reacted 72 hours at 10 DEG C, decompression rotary evaporation removes Mixed solvent, wash and double eugenols -1,1,3,3- tetra isopropyl disiloxane compounds, yield 85% are obtained after drying.
(2) double eugenol -1,1,3,3- tetra isopropyl disiloxane compounds of the above-mentioned preparations of 0.1mol are dissolved in 250mL 0.11mol 1,7- heptamethylene diamines and 0.55mol paraformaldehydes are added after dioxane solution, 60 DEG C are reacted 30 hours, are evaporated under reduced pressure Mixed solvent is removed, is dried to obtain double eugenols -1,1,3,3- tetra isopropyl disiloxanes-heptamethylene diamine organosilicon benzoxazine is pre- Polymers, shown in its structure such as formula (1-6), yield 94%.
By double eugenol -1,1,3,3- tetra isopropyl disiloxanes-heptamethylene diamine organosilicon benzoxazine prepolymer 500W Box uv cure machine carry out UV solidifications, obtain based on double eugenols -1,1,3,3- tetra isopropyl disiloxanes-heptamethylene diamine The cured product of organosilicon benzoxazine prepolymer.The stretch modulus of the cured product of gained is 1841MPa, and elongation at break is 11.0%, tensile strength 88MPa, Td10For 433 DEG C.
Embodiment 5
(1) by 0.5mol eugenols, 0.21mol diphenyl silanes, 0.05mol Speier catalyst, it is dissolved in 500mL In the mixed solution of dioxane and ethanol, reacted 1 hour at 100 DEG C, decompression rotary evaporation remove mixed solvent, washing and Double eugenol-diphenylsilane compounds, yield 89% are obtained after drying.
(2) double eugenol-diphenylsilane compounds of the above-mentioned preparations of 0.1mol are dissolved in 450mL dioxane and toluene Mixed solution after add 0.12mol hexamethylene diamines and 0.48mol paraformaldehydes, 70 DEG C are reacted 3 hours, are evaporated under reduced pressure and are removed mixing Solvent, it is dried to obtain double eugenol-diphenyl silane-hexamethylene diamine organosilicon benzoxazine prepolymers, its structure such as formula (1-7) institute Show, yield 97%.
Box UV-curing by double eugenol-diphenyl silanes-hexamethylene diamine organosilicon benzoxazine prepolymer with 500W Change machine carries out UV solidifications, obtains the solidification production based on double eugenol-diphenyl silanes-hexamethylene diamine organosilicon benzoxazine prepolymer Thing.The stretch modulus of the solidfied material of gained is 2130MPa, elongation at break 6.0%, tensile strength 101MPa, Td10For 427℃。
Embodiment 6
(1) by 0.5mol eugenols, 0.05mol diphenyl silanes, 0.04mol Karstedt catalyst, it is dissolved in In the mixed solution of 500mL dioxane and ethanol, being reacted 9 hours at 100 DEG C, decompression rotary evaporation removes mixed solvent, Wash and double eugenol-diphenylsilane compounds, yield 81% are obtained after drying.
(2) double eugenol-diphenylsilane compounds of the above-mentioned preparations of 0.1mol are dissolved in 737mL dioxane and toluene Mixed solution after add 0.11mol butanediamine and 0.60mol paraformaldehydes, 75 DEG C are reacted 3.4 hours, be evaporated under reduced pressure remove it is mixed Bonding solvent, it is dried to obtain double eugenol-diphenyl silane-butanediamine organosilicon benzoxazine prepolymers, its structure such as formula (1-8) It is shown, yield 93%.
Box UV-curing by double eugenol-diphenyl silanes-butanediamine organosilicon benzoxazine prepolymer with 500W Change machine carries out UV solidifications, obtains the solidification production based on double eugenol-diphenyl silanes-butanediamine organosilicon benzoxazine prepolymer Thing.The stretch modulus of the solidfied material of gained is 3935MPa, elongation at break 3.0%, tensile strength 150MPa, Td10For 438℃。
Embodiment 7
(1) 0.5mol eugenols, 0.1mol 1,1,3,3,5,5- hexam ethylcyclotrisiloxanes, 0.05molSpeier are catalyzed Agent, it is dissolved in the mixed solution of 500mL dioxane and ethanol, is reacted 0.5 hour at 100 DEG C, decompression rotary evaporation is gone Except mixed solvent, double eugenols -1,1,3,3,5,5- hexam ethylcyclotrisiloxane compounds are obtained after washing and drying, yield is 93%.
(2) double eugenol -1,1,3,3,5,5- hexam ethylcyclotrisiloxane compounds of the above-mentioned preparations of 0.1mol are dissolved in 0.12mol butanediamine and 0.48mol paraformaldehydes are added after the mixed solution of 350mL dioxane and toluene, 60 DEG C of reactions 5 are small When, it is evaporated under reduced pressure and removes mixed solvent, be dried to obtain double eugenols -1,1,3,3,5,5- hexam ethylcyclotrisiloxanes-butanediamine has Machine silicon benzoxazine prepolymer, shown in its structure such as formula (1-9), yield 98%.
Double eugenol -1,1,3,3,5,5- hexam ethylcyclotrisiloxanes-butanediamine organosilicon benzoxazine prepolymer is used 500W box uv cure machine carries out UV solidifications, obtains based on double eugenols -1,1, and 3,3,5,5- hexam ethylcyclotrisiloxanes - The cured product of butanediamine organosilicon benzoxazine prepolymer.The stretch modulus of the cured product of gained is 2036MPa, and fracture is stretched Long rate is 9.8%, tensile strength 68MPa, Td10For 437 DEG C.
Embodiment 8
(1) by 0.5mol eugenols, 0.08mol 1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxanes, 0.005mol Karstedt catalyst, it is dissolved in the mixed solution of 500mL dioxane and ethanol, is reacted 6 hours at 100 DEG C, is depressurized Rotary evaporation removes mixed solvent, washes and double eugenol-diphenylsilane compounds, yield 87% are obtained after drying.
(2) it is double eugenol -1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxane compounds of the above-mentioned preparations of 0.1mol are molten 0.11mol ethylenediamines and 0.48mol paraformaldehydes, 100 DEG C of reactions are added after the mixed solution of 230mL dioxane and toluene 2 hours, it is evaporated under reduced pressure and removes mixed solvent, is dried to obtain double eugenols -1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxane-second Diamines organosilicon benzoxazine prepolymer, shown in its structure such as formula (1-10), yield 99%.
By double eugenol -1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxanes-ethylenediamine organosilicon benzoxazine prepolymer UV solidifications are carried out with 500W box uv cure machine, are obtained based on double eugenols -1,1,1,3,5,7,7,7- prestox four The cured product of siloxanes-ethylenediamine organosilicon benzoxazine prepolymer.The stretch modulus of the cured product of gained is 1486MPa, elongation at break 11.0%, tensile strength 64MPa, Td10For 428 DEG C.
Embodiment 9
(1) by 0.5mol eugenols, the siloxanes of 0.08mol 1,1,3,3,5,5,7,7,9,9- decamethyls five, 0.004mol Speier catalyst, it is dissolved in the mixed solution of 500mL dioxane and ethanol,
Reacted 8 hours at 80 DEG C, decompression rotary evaporation removes mixed solvent, washing and obtain after drying double eugenols- The silicone compounds of 1,1,3,3,5,5,7,7,9,9- decamethyl five, yield 85%.
(2) by double silicone compounds of eugenol -1,1,3,3,5,5,7,7,9,9- decamethyls five of the above-mentioned preparations of 0.1mol Thing adds 0.1mol hexamethylene diamines and 0.6mol paraformaldehydes after being dissolved in the mixed solution of 300mL dioxane and toluene, and 110 DEG C anti- Answer 1.5 hours, be evaporated under reduced pressure and remove mixed solvent, be dried to obtain double eugenols -1,1,3,3,5,5,7,7,9,9- decamethyls five Siloxanes-hexamethylene diamine organosilicon benzoxazine prepolymer, shown in its structure such as formula (1-11), yield 97%.
Five siloxanes of double eugenol -1,1,3,3,5,5,7,7,9,9- decamethyls-hexamethylene diamine organosilicon benzoxazine is pre- Polymers carries out UV solidifications with 500W box uv cure machine, obtains based on double eugenols -1,1,3,3,5,5,7,7,9,9- The cured product of five siloxanes of decamethyl-hexamethylene diamine organosilicon benzoxazine prepolymer.The stretch modulus of the cured product of gained For 1446MPa, elongation at break 14.0%, tensile strength 78MPa, Td10For 423 DEG C.
Above-mentioned is that the present invention is elaborated in conjunction with the embodiments, but embodiments of the present invention are not by above-mentioned implementation The limitation of example, other any changes made under patent core guiding theory of the present invention, replacement, combine simplified etc. be included in Within the protection domain of patent of the present invention.

Claims (9)

1. a kind of organosilicon benzoxazine resin prepolymer based on eugenol, it is characterised in that there is the knot as shown in formula (I) Structure：
In formula (I), n is integer, R1Selected from the substituent as shown in formula (1)~(7),
R2Selected from C2H4、C3H6、C4H8、C5H10、C6H4、C6H12、C7H14And C8H16At least one of.
2. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, including：
(1) organic silicon monomer of eugenol and more hydrogen-baseds end-blocking is occurred hydrosilylation, tied under catalyst action Eugenol organo-silicon compound of the structure as shown in formula (II)；
In formula (II), R1Selected from the substituent as shown in formula (1)~(7),
(2) by eugenol organo-silicon compound, diamines and paraformaldehyde be blended, under heating under the conditions of polymerisation occurs, make It is standby to obtain the organosilicon benzoxazine resin prepolymer based on eugenol.
3. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is that the organic silicon monomer of more hydrogen-based end-blockings is 1,1,3,3- tetramethyl disiloxane, 1,3,5,7- tetramethyl tetrahydrochysenes Cyclotetrasiloxane, 1,1,3,3,5,5- hexam ethylcyclotrisiloxanes, 1,1,1,3,5,7,7,7- octamethylcyclotetrasiloxanes, 1,1,3,3, The siloxanes of 5,5,7,7,9,9- decamethyls five, diphenyl silane, 1,1,3,3- tetra isopropyl disiloxanes or 1,1,5,5- tetramethyls Base -3,3- diphenyl trisiloxanes.
4. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, in step (1), the mol ratio of the eugenol and the organic silicon monomer of more hydrogen-baseds end-blocking is 1~20：1.
5. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, in step (1), the temperature of the hydrosilylation is 10~120 DEG C, and the reaction time is 0.5~72h.
6. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, in step (1), the dosage of catalyst is the 0.1~10% of the amount of eugenol material.
7. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, in step (2), the mol ratio of the eugenol organo-silicon compound, diamines and paraformaldehyde is 1：1~1.2：4~ 6。
8. the preparation method of the organosilicon benzoxazine resin prepolymer according to claim 1 based on eugenol, it is special Sign is, in step (2), the temperature of the polymerisation is 0~120 DEG C, 0.5~70h of reaction time.
9. the organosilicon benzoxazine resin prepolymer based on eugenol described in a kind of any one of claim 1~8 is in high temperature Application in bonding agent.
CN201710257910.1A 2017-04-19 2017-04-19 A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol Active CN107417870B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710257910.1A CN107417870B (en) 2017-04-19 2017-04-19 A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710257910.1A CN107417870B (en) 2017-04-19 2017-04-19 A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol

Publications (2)

Publication Number Publication Date
CN107417870A true CN107417870A (en) 2017-12-01
CN107417870B CN107417870B (en) 2019-06-18

Family

ID=60424133

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710257910.1A Active CN107417870B (en) 2017-04-19 2017-04-19 A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol

Country Status (1)

Country Link
CN (1) CN107417870B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020054218A1 (en) * 2018-09-14 2020-03-19 積水化学工業株式会社 Benzoxazine compound, curable resin composition, adhesive, adhesive film, cured object, circuit board, interlayer dielectric material, and multilayered printed wiring board

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105503674A (en) * 2015-12-03 2016-04-20 中国科学院宁波材料技术与工程研究所 Eugenol based polyfunctional unsaturated monomers as well as preparation method and application thereof
CN106631942A (en) * 2016-12-08 2017-05-10 中国科学院宁波材料技术与工程研究所 Eugenol-based UV (ultraviolet) optical resin monomer and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105503674A (en) * 2015-12-03 2016-04-20 中国科学院宁波材料技术与工程研究所 Eugenol based polyfunctional unsaturated monomers as well as preparation method and application thereof
CN106631942A (en) * 2016-12-08 2017-05-10 中国科学院宁波材料技术与工程研究所 Eugenol-based UV (ultraviolet) optical resin monomer and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PERIYASAMY THIRYKUMARAN ET AL.: "Synthesis of Eugenol-Based Polybenzoxazine–POSS Nanocomposites for Low Dielectric Applications", 《POLYMER COMPOSITES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020054218A1 (en) * 2018-09-14 2020-03-19 積水化学工業株式会社 Benzoxazine compound, curable resin composition, adhesive, adhesive film, cured object, circuit board, interlayer dielectric material, and multilayered printed wiring board
CN112533906A (en) * 2018-09-14 2021-03-19 积水化学工业株式会社 Benzoxazine compound, curable resin composition, adhesive film, cured product, circuit board, interlayer insulating material, and multilayer printed wiring board
JPWO2020054218A1 (en) * 2018-09-14 2021-08-30 積水化学工業株式会社 Benzoxazine compounds, curable resin compositions, adhesives, adhesive films, cured products, circuit boards, interlayer insulating materials, and multilayer printed wiring boards
JP7474054B2 (en) 2018-09-14 2024-04-24 積水化学工業株式会社 Benzoxazine compound, curable resin composition, adhesive, adhesive film, cured product, circuit board, interlayer insulating material, and multilayer printed wiring board

Also Published As

Publication number Publication date
CN107417870B (en) 2019-06-18

Similar Documents

Publication Publication Date Title
Demir et al. Thermally curable main-chain benzoxazine prepolymers via polycondensation route
Zhuo et al. Flame retardancy and flame retarding mechanism of high performance hyperbranched polysiloxane modified bismaleimide/cyanate ester resin
CN109749086B (en) Self-repairing organic silicon elastomer based on dynamic disulfide bond and preparation method thereof
CN105694047B (en) Main chain silicon modified organic polymer containing cyclic structure and preparation method thereof
CN106947059A (en) High-temp resistant fire-retarding epoxy resin and its preparation method and application of the vanilla aldehyde radical rich in phenyl ring
CN107573496A (en) A kind of furandicarboxylic acid polyester containing benzoxazine structure and its preparation method and application
CN108164708B (en) Preparation method of fluorescent polysiloxane-benzoxazine-based self-repairing elastomer material
Dong et al. Preparation and characterization of 3-chloropropyl polysiloxane-based heat-curable silicone rubber using polyamidoamine dendrimers as cross-linkers
CN108252102A (en) The silicon rubber leather and its coating process of a kind of UV resistant and hydrolysis
Sun et al. Recent advances in carborane-siloxane polymers
CN107417870B (en) A kind of organosilicon benzoxazine resin prepolymer and its preparation method and application based on eugenol
Fu et al. Preparation and properties of hybrid materials originating from polybenzoxazines and silsesquioxanes
Othman et al. The effects of the SiOSi segment presence in BAPP/BPDA polyimide system on morphology and hardness properties for opto-electronic application
CN105837617A (en) Preparation and application of trifluorovinyl-ether-containing cyclosiloxane capable of direct heat curing
CN105384912B (en) A kind of itaconic acid basic ring shape silicon skeletal epoxy resin, preparation method and its application of coating is prepared as matrix resin
Zhang et al. Synthesis of allyl‐ended hyperbranched organic silicone resin by halloysite‐supported platinum catalyst
Zhou et al. Synthesis and properties of silicon‐containing arylacetylene resins with polyhedral oligomeric silsesquioxane
Pan et al. Synthesis of siloxanes containing vinyl and epoxy group and its enhancement for adhesion of addition-cure silicone encapsulant
Hu et al. Preparation and properties of maleimide‐functionalized hyperbranched polysiloxane and its hybrids based on cyanate ester resin
Zhao et al. Preparation and performance of phenyl-vinyl-POSS/addition-type curable silicone rubber hybrid material
CN100497407C (en) Aryne resin containing silicone
Chen et al. Synthesis, curing behavior and thermal properties of silicon‐containing hybrid polymers with Si− C≡ C units
Guo et al. Luminescent and robust perovskite–silicone elastomers prepared by light induced thiol–ene reaction
CN112126194B (en) Preparation method of toughened and modified epoxy resin composite material
Liu et al. Thermally Activated Delayed Fluorescence Polysiloxanes with Short Delay Fluorescence Lifetimes

Legal Events

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