CN107151309B - A kind of preparation method of carborane phenoxy resin - Google Patents
A kind of preparation method of carborane phenoxy resin Download PDFInfo
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- CN107151309B CN107151309B CN201710355644.6A CN201710355644A CN107151309B CN 107151309 B CN107151309 B CN 107151309B CN 201710355644 A CN201710355644 A CN 201710355644A CN 107151309 B CN107151309 B CN 107151309B
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
The present invention relates to a kind of preparation methods of carborane phenoxy resin.This method is using the bis-phenol of the structure containing carborane and low molecular weight difunctional epoxy compound as main reactant, and using propylene glycol phenylate as solvent, bis- (triphenylphosphine) ammonium chlorides are catalyst, has synthesized the high molecular weight phenoxy resin of different carborane contents.The advantages of synthetic method is: reaction condition is mild, controllable；Molecular weight of product is higher, and molecular weight is controllable；There is preferable compatibility with common low-molecular-weight epoxy resin, it can be epoxy resin toughened；Carborane content is controllable, has excellent thermal stability and high temperature carbon yield, high temperature bonding better performances.
Description
Technical field
The present invention relates to a kind of preparation methods of carborane phenoxy resin.This method is with the bis-phenol of the structure containing carborane and low
Molecular weight difunctional epoxy compound is main reactant, and using propylene glycol phenylate as solvent, bis- (triphenylphosphine) ammonium chlorides are to urge
Agent has synthesized the high molecular weight phenoxy resin of different carborane contents.
Background technique
Phenoxy resin belongs to a kind of thermoplastic epoxy and compares with epoxy resin, its molecular weight is bigger, in structure
Ratio very little, can be ignored shared by epoxy group.For a long time, epoxy polymer is all a kind of thermosetting polymer,
Because the various monomers that epoxy chemical is usually all various heat curing types can solidify and be cross-linked to form reticular structure, phenoxy resin by
It is larger in its molecular weight, it is solid under room temperature, therefore directly can make coating or adhesive with solvent dissolution.In addition, phenol oxygen
Resin and epoxy resin have good compatibility, and can usually be used to be added to can be with toughening after the solidification of addition curing agent in epoxy
Epoxy resin cured product.
Carborane is the polyhedral compound being made of three kinds of carbon, boron, hydrogen elements, and common structure is cage construction, cage
Formula structure makes it have very high thermal stability and chemical stability.Patent 201410209224 discloses a kind of carborane bis-phenol
The preparation method of diglycidyl ether is prepared for the double of the structure containing carborane with reacting for epoxychloropropane by carborane bis-phenol
Degree of functionality epoxy resin, after being solidified using DDS, glass transition temperature is respectively 175.8 DEG C and 167.6 DEG C, and TGA analysis is further
Show that the introducing of carborane structure greatly improves the thermal stability of epoxy resin.Han G,Yang Z,Yang X,Zhang X,
Jiang S,and Lu Y.Chinese Journal of Polymer Science 2016；34 (9): 1103-1116 report
The synthetic method of low molecular weight carborane novolac epoxy resin is urged in acidity first using carborane bis-phenol and formaldehyde as raw material
Thermoplasticity carborane phenolic resin is prepared under agent effect, then under the catalytic action of tetrabutylammonium bromide, with epoxy chlorine
Propane carries out epoxidation, finally obtains the polyfunctionality novolac epoxy resin of the structure containing carborane.After DDS and DDM solidification,
TGA is analysis shows the introducing of carborane greatly improves the high temperature carbon yield of novolac epoxy resin.
Summary of the invention
The purpose of the present invention is a kind of preparation method of carborane phenoxy resin, the advantages of synthetic method, is: reaction item
Part is mild, controllable；Molecular weight of product is higher, and molecular weight is controllable；There is preferable compatibility with common low-molecular-weight epoxy resin,
It can be epoxy resin toughened；Carborane content is controllable, have excellent thermal stability and high temperature carbon yield, high temperature bonding performance compared with
It is good.
Used catalyst of the present invention includes tetraethyl oxygen amine-oxides, tetraphenyl phosphonium bromide, and ethyl triphenyl acetic acid phosphorus is double
(triphenylphosphine) ammonium chloride.
Diphenol used in the present invention includes ortho position carborane bis-phenol, and meta position carborane bis-phenol aligns carborane bis-phenol, bisphenol-A
O- benzenediol, m- benzenediol, p- benzenediol, 1,5- naphthalenediol.
Low-molecular-weight epoxy resin used in the present invention includes bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, phenol
Formaldehyde epoxy resin, ortho position carborane epoxy resin, meta position carborane epoxy resin.
Carborane phenoxy resin composition principle is that reaction is nucleophilic ring opening reaction process of the phenol to epoxy group, the present invention with
By one-step method prepared by macromolecule for raw material to ortho position carborane phenol and carborane epoxy resin and bisphenol A diglycidyl ether
Molecular weight carborane phenoxy resin.It uses its derivative of triphenylphosphine as catalyst, first makes anion and carbon boron in catalyst
Alkane epoxy carries out opening and generates alcoxyl intermediate.Then it is reacted again with phenol and generates phenoxy resin.Alkoxy and hydroxyl
Continue polymerization increase the degree of polymerization.The molecular weight of prepolymer can be adjusted by the size of epoxy and the molar ratio of bis-phenol.
By taking bisphenol A diglycidyl ether synthesizes carborane phenoxy resin with ortho position carborane diphenol as an example, reaction equation is stated
It is as follows:
Material proportion is as shown in the table:
Synthetic reaction the following steps are included:
Bis-phenol, the low molecular weight difunctional epoxide of the structure containing carborane are added into the flask equipped with magneton for the first step
Object and triphenylphosphine derivates are closed, the molar ratio of three kinds of materials is 1:(0.80-1.02): 0.01；Solvent third is added in reaction flask
Glycol phenylate, dosage are so that the amount of substance concentration of bis-phenol is 0.798mol/L；Nitrogen is passed through in reaction flask, stirring makes reactant
Dissolution in a solvent, heating, system 160-180 DEG C of reaction 12-24h under stiring；
Second step is cooled to 150 DEG C, and 4-TBP is added into reaction flask, and dosage is bis-phenol dosage
Then 13.69mol% continues isothermal reaction 1h under nitrogen protection；
Third step, reaction was completed, after material is cooled to room temperature, DMF is added with dilute reaction solution, then reaction solution is added dropwise
Into methanol/deionized water mixed solvent (volume ratio 1:1) of zero degree, the thick white substance of precipitation is collected by filtration, at room temperature
It is drying for one day.Then it is placed in 2h in 120 DEG C of vacuum oven again, obtains crude product.Crude product is dissolved in THF, and zero is added dropwise again
It is purified in the methanol of degree/deionized water mixed solvent (volume ratio 1:1), collects, dries, it is solid to finally obtain white plates
Body.
The molecular weight of gained carborane phenoxy resin and its distribution are by epoxy and bis-phenol proportion, reaction temperature, reaction time
It controls, generally requiring the amount of epoxy is 0.8-1.02 times of bis-phenol.The molecular weight of carborane phenoxy resin is higher, is solid
Body can be used alone can also be crosslinked with curing agent.
The resulting carborane phenoxy resin synthetic method of the present invention is simple, and epoxy pollution is small, can be direct after being dissolved with solvent
As coating or adhesive, curing agent can be added well with the compatibility of ordinary epoxy resin and carry out solidification crosslinking, solidfied material is resistance to
Hot property greatly improves, and can be used as high-temperature resistance adhesive and coating.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment to this hair
It is bright to be explained in detail, but practical range of the invention is not limited.
Embodiment 1
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.09mL in 25mL round bottom reaction tube
0.4489g (1.3686mmol) o- carborane biphenol and 0.00785g is then added in glycol phenylate (PGPE)
(0.01368mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react for 24 hours system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.02816g (0.1874mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 11900, molecular weight distribution (MW/ Mn) it is 2.23, yield
85.6%.1H NMR (400MHz, CDCl3), δ (TMS, ppm): 7.47 (d, H), 7.09 (d, H), 6.09 (s, 2H), 6.77 (m,
H), 4.19 (m, H), 4.02 (s, H), 3.05 (m, H), 3.70 (m, H), 1.22-3.12 (m, 10H), 2.16 (s, 2H) .13C
NMR (100MHz, CDCl3): 159.8,143.6,132.2,129.5,127.7,123.4,114.1,85.5,73.5,73.2,
68.5,42.2,30.9
Embodiment 2
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.4489g (1.396mmol) o- carborane biphenol and 0.00801g is then added in glycol phenylate (PGPE)
(0.01396mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react for 24 hours system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.02872g (0.1912mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 12100, molecular weight distribution (MW/ Mn) it is 2.22, yield
85.9%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 3
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added in glycol phenylate (PGPE)
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react for 24 hours system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 12300, molecular weight distribution (MW/ Mn) it is 2.13, yield
86.2%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 4
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added in glycol phenylate (PGPE)
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 170 DEG C of magnetons are stirred to react for 24 hours system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 12200, molecular weight distribution (MW/ Mn) it is 2.17, yield
86.6%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 5
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added in glycol phenylate (PGPE)
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 170 DEG C of magnetons are stirred to react for 24 hours system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 12600, molecular weight distribution (MW/ Mn) it is 2.17, yield
87.1%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 6
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in 1.11mL in 25mL round bottom reaction tube by 1.00
Propylene glycol phenylate (PGPE), 0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react 12h to system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.Be added dropwise to 400ml zero degree volume ratio be one to one deionized water and
In the mixed solution of methanol, purifying, collecting is dry.Obtain white strip solid, weight average molecular weight (MW) it is 12500, molecular weight
It is distributed (MW/ Mn) it is 2.12, yield 85.9%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 7
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added in glycol phenylate (PGPE)
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react 16h to system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 9900, molecular weight distribution (MW/ Mn) it is 2.33, yield 83.5%.
Nuclear-magnetism characterization result is same as Example 1.
Embodiment 8
0.5368g (1.396mmol) bisphenol A diglycidyl ether is dissolved in the third of 1.11mL in 25mL round bottom reaction tube
0.5731g (1.745mmol) o- carborane biphenol and 0.00101g is then added in glycol phenylate (PGPE)
(0.01745mmol) bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 160 DEG C of magnetons are stirred to react 20h to system under nitrogen protection, later
It is cooled to 150 DEG C plus 0.03591g (0.2391mmol) terminator 4-TBP, the reaction was continued 1h is diluted with 1mL DMF
Afterwards, in the mixed solution of deionized water and methanol that the volume ratio for stirring and being added dropwise to 400ml zero degree is one to one.It separates
The thick white object of precipitation, it is drying for one day under air.2h is dried in vacuo at 120 DEG C in a vacuum drying oven, uses THF after processing again
Dissolution is added dropwise to the volume ratio of 400ml zero degree as in one to one deionized water and the mixed solution of methanol, purifying, collecting is dry
It is dry.Obtain white strip solid, weight average molecular weight (MW) it is 10200, molecular weight distribution (MW/ Mn) it is 2.335, yield
86.2%.Nuclear-magnetism characterization result is same as Example 1.
Embodiment 9
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 1.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
30.2%.
Embodiment 10
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 9
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 76.3MPa, elongation at break 7.57%；Tensile strength is 73.2MPa, elongation at break 6.67% at 180 DEG C.
Embodiment 11
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 2.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
31.1%.
Embodiment 12
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 11
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 76.5MPa, elongation at break 7.67%；Tensile strength is 74.3MPa, elongation at break 6.73% at 180 DEG C.
Embodiment 13
Carborane phenoxy resin prepared with embodiment 3 mutually infiltrates row curing reaction with low molecule bisphenol A epoxide resin.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
31.4%.
Embodiment 14
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 13
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 76.1MPa, elongation at break 7.61%；Tensile strength is 73.3MPa, elongation at break 6.68% at 180 DEG C.
Embodiment 15
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 4.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
31.7%.
Embodiment 16
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 15
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 77.2MPa, elongation at break 7.68%；Tensile strength is 74.1MPa, elongation at break 6.71% at 180 DEG C.
Embodiment 17
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 5.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
31.8%.
Embodiment 18
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 17
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 77.9MPa, elongation at break 7.72%；Tensile strength is 74.1MPa, elongation at break 6.75% at 180 DEG C.
Embodiment 19
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 6.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
32.2%.
Embodiment 20
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 19
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 77.2MPa, elongation at break 7.59%；Tensile strength is 75.2MPa, elongation at break 6.62% at 180 DEG C.
Embodiment 21
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 7.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
31.4%.
Embodiment 22
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 21
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 77.3MPa, elongation at break 7.54%；Tensile strength is 73.6MPa, elongation at break 6.58% at 180 DEG C.
Embodiment 23
Row curing reaction is mutually infiltrated with low molecule bisphenol A epoxide resin with carborane phenoxy resin prepared by embodiment 8.?
0.08g carborane phenoxy resin and E51 epoxy resin 3g are added in two mouth flask, consolidating for 1.2g is added in another two mouth flask
4.4 diaminodiphenylmethane of agent (DDM), being separately added into tetrahydrofuran dissolves the two.Magneton is added into flask, is stirring
It mixes the condition that temperature is 35 DEG C and stirs 1h.Then resin solution and curing agent solution are mixed evenly, were placed at room temperature
Night removes tetrahydrofuran solvent with abundant volatilization, is then placed into air dry oven, be heating and curing 2h at 80 DEG C, is warming up to
150 DEG C, the product after obtaining crosslinking curing.Thermogravimetic analysis (TGA) (TG): the carbon yield after 900 DEG C of ablations is in a nitrogen atmosphere
32.1%.
Embodiment 24
Tensile property survey is carried out to the solidfied material of carborane bis-phenol phenoxy resin and E51 epoxy resin made from embodiment 23
Examination, referring to national standard GB/T 2567-2008, specimen size is 50mm × 2mm × 0.05mm, as a result as follows: tensile strength at 23 DEG C
For 77.4MPa, elongation at break 7.52%；Tensile strength is 73.1MPa, elongation at break 6.41% at 180 DEG C.
Claims (3)
1. a kind of method for preparing carborane phenoxy resin, which is characterized in that specifically includes the following steps:
Bis-phenol, difunctional epoxy compound and the triphenyl of the structure containing carborane are added into the flask equipped with magneton for the first step
Phosphine-derivatives, the molar ratio of three kinds of materials are 1:(0.80-1.02): 0.01；Solvent propylene glycol phenylate, dosage are added in reaction flask
To make the substance withdrawl syndrome of bis-phenol be 0.798mol/L；Nitrogen is passed through in reaction flask, stirring makes reactant be dissolved in solvent
In, heating, system 160-180 DEG C of reaction 12-24h under stiring；
Second step is cooled to 150 DEG C, and 4-TBP is added into reaction flask, and dosage is the 13.69mol% of bis-phenol dosage,
Then continue isothermal reaction 1h under nitrogen protection；
Third step, reaction was completed, after material is cooled to room temperature, DMF is added with dilute reaction solution, reaction solution is then added drop-wise to zero
Volume ratio 1:1 methanol/deionized water in the mixed solvent of degree, is collected by filtration the thick white substance of precipitation, dries one at room temperature
It；Then it is placed in 2h in 120 DEG C of vacuum oven again, obtains crude product；Crude product is dissolved in THF, is added drop-wise to volume ratio again
It purified, collected, dried for 1:1 methanol/deionized water in the mixed solvent, finally obtain white flaky solid.
2. according to the preparation method of claim 1, which is characterized in that the bis-phenol is that o- carborane bis-phenol or m- carborane are double
Phenol.
3. according to the preparation method of claim 1, which is characterized in that the difunctional epoxy compound is the shrink of bisphenol-A two
Glycerin ether, o- carborane bisphenol diglycidyl or m- carborane bisphenol diglycidyl.
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| CN1884343A (en) * | 2006-06-02 | 2006-12-27 | 华东理工大学 | Novel carborane- (siloxane or silane)- ethinyl high temperature resistant polymer and its preparation method |
| CN103992463B (en) * | 2014-05-17 | 2015-12-30 | 北京化工大学 | The synthesis of carborane epoxy resin and curing |
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| Title |
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| "Synthesis, Characterization and Thermal Stability of Novel Carborane-Containing Epoxy Novolacs";Guo Han et al.;《Chinese Journal of Polymer Science》;20160728;第34卷(第9期);第1103-1116页 * |
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