CN107699191A - A kind of waterproof heat-resisting adhesive and preparation method thereof - Google Patents
A kind of waterproof heat-resisting adhesive and preparation method thereof Download PDFInfo
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- CN107699191A CN107699191A CN201711010968.2A CN201711010968A CN107699191A CN 107699191 A CN107699191 A CN 107699191A CN 201711010968 A CN201711010968 A CN 201711010968A CN 107699191 A CN107699191 A CN 107699191A
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- 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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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Abstract
The present invention relates to field of adhesive technology, discloses a kind of waterproof heat-resisting adhesive and preparation method thereof.The raw material that the adhesive is matched by following parts by weight is made：18 ~ 22 parts of 50 ~ 70 parts of modified hydroxyl acrylic resin, 25 ~ 30 parts of modified organic silicone resin, 2 ~ 4 parts of dimethylbenzene, 3 ~ 8 parts of tributyl phosphate, 1 ~ 4 part of hydroquinones, 2 ~ 6 parts of polyetheramine, 1 ~ 4 part of VTES and flake asbestos.Invention adhesive has good waterproof heat-resisting performance.
Description
Technical field
The present invention relates to field of adhesive technology, more particularly, to a kind of waterproof heat-resisting adhesive and preparation method thereof.
Background technology
It is gluing to refer to homogeneity or technology that heterogeneous body surface is linked together with adhesive, have that stress distribution is continuous,
The features such as in light weight, or sealing, most technological temperatures are low.It is gluing especially suitable for unlike material, different-thickness, ultra-thin specification and
The connection of complex component.Gluing RECENT DEVELOPMENTS is most fast, and application industry is extremely wide, and to high-and-new science and technology progress and the daily life of the people
Improvement living has significant impact.Therefore, it is particularly significant to study, develop and produce all kinds of adhesive.The properties of adhesive determine
The Storage period of the extensive degree, especially adhesive of its application, directly determines its use cost and effect.Adhesive point
For inorganic adhesive and organic adhesion agent, although inorganic adhesive with higher resistance to elevated temperatures and higher intensity,
Fragility is big, and the risk that seal failure is connected in shock and vibration environment is larger；General polymerization thing have it is preferably flexible, can be with
Overcome inorganic adhesive fragility big, the shortcomings that intolerant to shock and vibration.But when adhesive applications are in humidity or frequent with water
When in the environment of contact, adhesive is easy to hydrolyze, and adhesive is lost plybonding effect, and existing adhesive is intolerant to height in addition
Temperature, in use, the decomposition of adhesive can be caused in hot environment.
The content of the invention
The present invention is that existing adhesive water proofing property is poor, technical problem of non-refractory in order to overcome, there is provided one kind has anti-
The resistant to elevated temperatures adhesive of water.
Present invention also offers a kind of preparation method of waterproof heat-resisting adhesive.
To achieve these goals, the present invention uses following technical scheme：A kind of water proof fire retardant adhesive, by following weight
The raw material of number proportioning is made：50~70 parts of modified hydroxyl acrylic resin, 25~30 parts of modified organic silicone resin, dimethylbenzene 2
~4 parts, 3~8 parts of tributyl phosphate, 1~4 part of hydroquinones, 2~6 parts of polyetheramine, 1~4 part of VTES and
18~22 parts of flake asbestos.
The use of modified hydroxyl acrylic resin and modified organic silicone resin is sticky matter；Flake asbestos is filler；Polyetheramine
For curing agent, the hardening time of adhesive can be shortened；Dimethylbenzene is diluent, the more sticky adhesive of dilution, and increase is each
The uniformity mixed between component；Tributyl phosphate is plasticizer；Hydroquinones is high-temperature stabilizer, it is possible to increase adhesive is in height
Stability under the conditions of temperature, suppress the decomposition of adhesive；VTES is coupling agent, by increasing capacitance it is possible to increase flake asbestos exists
Dispersiveness and uniformity agent in component.
Preferably, the preparation method of the modified hydroxyl acrylic resin comprises the following steps：
(1) 110~120mL dioxane and 0.02~0.05mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen
Gas, 55~65 DEG C are then heated to, then hydroxy acrylic acid is added in four-hole bottle, stirred 50~60min, obtain hydroxyl third
Olefin(e) acid resin prepolymer；
(2) 3~4mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5~6, rise
Then temperature adds 0.4~0.6mol MethylethoxylsiliconFluid Fluids, 40~60min of stirring reaction to 60~70 DEG C；
(3) 0.08~0.12mol benzoyl peroxides are first added into the reaction solution of step (2), then it is slowly added dropwise 0.4~
0.6mol modified methacrylic acid trifluoro ethyl esters, 40~50min of stirring reaction.
The present invention has carried out hydrophobically modified to Hydroxylated acrylic resin, and MethylethoxylsiliconFluid Fluid exists with Hydroxylated acrylic resin
Graft reaction occurs in the presence of initiator azodiisobutyronitrile, the polymer of formation has relatively low surface energy, hydrophobic performance
Improve；Polymerisation, modified methacrylic acid trifluoro second are occurred into for modified methacrylic acid trifluoro ethyl ester and above-mentioned polymer again
Ester contains the stronger carbon-fluorine bond of hydrophobicity, has stronger hydrophobic performance, further increases the hydrophobic of Hydroxylated acrylic resin
Performance.
Preferably, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 180~200mL deionized waters are added into four-hole bottle, then add 0.15~0.25mol sodium alkyl benzene sulfonates and 0.8~
0.15mol ammonium persulfates are passed through the air in nitrogen discharge four-hole bottle, are then stirred 30~60min；
(b) 0.4~0.6mol trifluoroethyl methacrylates and 0.3~0.4mol propylene are added in the solution into step (a)
Acetoacetic ester, 3~5h is stirred, then heat to 65~75 DEG C, react 30~50min, then be cooled to 35~40 DEG C, obtain being modified first
Base acrylic acid trifluoro ethyl ester.
Trifluoroethyl methacrylate is directly undesirable with hydroxy acrylic acid performed polymer generation polymerisation effect, Zhi Nengsheng
Into the macromolecule polyalcohol of a small amount of trifluoroethyl methacrylate and hydroxy acrylic acid, first using ethyl acrylate to methyl-prop
Olefin(e) acid trifluoro ethyl ester enters modification, and the polymer of generation has preferable reactivity, fully can polymerize with hydroxy acrylic acid
Reaction；In addition, being entered using ethyl acrylate to trifluoroethyl methacrylate modified, the polymer of generation has preferably viscous
Property, add the adhesive property of Hydroxylated acrylic resin.
Preferably, the preparation method of the modified organic silicone resin comprises the following steps：
(1) 15~25g trim,ethylchlorosilanes and 5~9g ethyl chlorosilanes are added to 60~80mL dimethyl formamide solutions
In, stir at normal temperatures 1~2 hour, then adding 5~9g dichloro-diethyl silanes, stirring 40~50 minutes, obtain chlorine silicon
Alkane mixed liquor；
(2) 50~60mL methanol and 12~16mL dichloromethane are added in 150~180mL distilled water, it is warming up to 55~
60 DEG C, chlorosilane mixed liquor is then added, stirs 2~3 hours, obtains organic-silicone prepolymer solution；
(3) 6~10g flyash is added in 80~90mL methanol solutions, then adds the organic siliconresin that step (2) obtains
Prepolymer solution, it is stirred 3~5 hours, obtains modified organic silicone resin.
The skeleton structure of organic siliconresin in flyash is Si-O-Si, and Si-O has larger bond energy, in the bar of high temperature
Easy fracture and decomposition are not allowed under part, therefore there is excellent heat-resisting quantity and stability；It is carried out further using flyash
It is heat resistance modified, the silica in flyash contains hydroxyl, and the hydroxyl in organosilicon can be with the hydroxyl of silica surface
Polycondensation reaction is freeed, improves the degree of cross linking of organosilicon, further enhancing the heat resistance of organosilicon；Silica and organosilicon
The polymer formed after crosslinking has certain colloidal nature, possesses certain adsorption capacity, can substantially reduce consolidating for adhesive
Change temperature and shorten the hardening time of adhesive.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred；
(B) temperature of reaction kettle is increased to 70~80 DEG C, the dimethylbenzene, tricresyl phosphate fourth of formulation weight part is added into reactor
Ester, hydroquinones, polyetheramine, are then sufficiently stirred again；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Preferably, mixing speed is 140~160r/min in the step (A), mixing time is 50~60min.
Preferably, mixing speed is 120~150r/min in the step (B), mixing time is 1~2h.
Therefore, the present invention has the advantages that：(1) MethylethoxylsiliconFluid Fluid and Hydroxylated acrylic resin are in initiator
Graft reaction occurs in the presence of azodiisobutyronitrile, the polymer of formation has relatively low surface energy, and hydrophobic performance improves；
(2) modified methacrylic acid trifluoro ethyl ester contains the stronger carbon-fluorine bond of hydrophobicity, has stronger hydrophobic performance, further improves
The hydrophobic performance of Hydroxylated acrylic resin；(3) modified, generation is entered to trifluoroethyl methacrylate using ethyl acrylate
Polymer have preferably viscosity, add Hydroxylated acrylic resin adhesive property (4) add hydroquinones high-temperature stable
Agent, it is possible to increase the stability of adhesive under the high temperature conditions, suppress the decomposition of adhesive；(5) organic siliconresin has larger
Bond energy, easy fracture and decomposition are not allowed under conditions of high temperature, therefore there is excellent heat-resisting quantity and stability；(6) utilize
Flyash carries out further heat resistance modified to it, further enhancing the heat resistance of organosilicon；(7) silica with it is organic
The polymer formed after silicon crosslinking has certain colloidal nature, possesses certain adsorption capacity, can substantially reduce adhesive
Solidification temperature and the hardening time for shortening adhesive.
Embodiment
Below by specific embodiment, technical scheme is described further.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art,
Method in embodiment, it is the conventional method of this area unless otherwise instructed.
Embodiment 1
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：50 parts of modified hydroxyl acrylic resin,
25 parts of modified organic silicone resin, 2 parts of dimethylbenzene, 3 parts of tributyl phosphate, 1 part of hydroquinones, 2 parts of polyetheramine, the ethoxy of vinyl three
18 parts of 1 part of base silane and flake asbestos.
Wherein, the preparation method of modified hydroxyl acrylic resin comprises the following steps：
(1) 110mL dioxane and 0.02mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen, be then heated to
55 DEG C, then hydroxy acrylic acid is added in four-hole bottle, stirs 50min, obtain Hydroxylated acrylic resin performed polymer；
(2) 3mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5, and rise temperature is extremely
60 DEG C, then add 0.4mol MethylethoxylsiliconFluid Fluids, stirring reaction 40min；
(3) 0.08mol benzoyl peroxides are first added into the reaction solution of step (2), 0.4mol is then slowly added dropwise and is modified first
Base acrylic acid trifluoro ethyl ester, stirring reaction 40min.
Wherein, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 180mL deionized waters are added into four-hole bottle, then add 0.15mol sodium alkyl benzene sulfonates and 0.8mol ammonium persulfates to lead to
Enter the air in nitrogen discharge four-hole bottle, be then stirred 30min；
(b) 0.4mol trifluoroethyl methacrylates and 0.3mol ethyl acrylates, stirring are added in the solution into step (a)
3h, 65 DEG C are then heated to, react 30min, then be cooled to 35 DEG C, obtain modified methacrylic acid trifluoro ethyl ester.
Wherein, the preparation method of modified organic silicone resin comprises the following steps：
(1) 15g trim,ethylchlorosilanes and 5g ethyl chlorosilanes are added in 60mL dimethyl formamide solutions, stirred at normal temperatures
Mix 1 hour, then adding 5g dichloro-diethyl silanes, stirring 40 minutes, obtain chlorosilane mixed liquor；
(2) 50mL methanol and 12mL dichloromethane are added in 150mL distilled water, are warming up to 55 DEG C, then add chlorine silicon
Alkane mixed liquor, stir 2 hours, obtain organic-silicone prepolymer solution；
(3) 6g flyash is added in 80mL methanol solutions, it is molten then adds the organic-silicone prepolymer that step (2) obtains
Liquid, it is stirred 3 hours, obtains modified organic silicone resin.
A kind of preparation method of waterproof heat-resisting adhesive, it is characterized in that, comprise the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred, mixing speed 140r/min, mixing time 50min；
(B) temperature of reaction kettle is increased to 70 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 120r/min, mixing time 1h；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Embodiment 2
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：55 parts of modified hydroxyl acrylic resin,
26 parts of modified organic silicone resin, 2 parts of dimethylbenzene, 4 parts of tributyl phosphate, 2 parts of hydroquinones, 3 parts of polyetheramine, the ethoxy of vinyl three
19 parts of 2 parts of base silane and flake asbestos.
Wherein, the preparation method of modified hydroxyl acrylic resin comprises the following steps：
(1) 112mL dioxane and 0.03mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen, be then heated to
58 DEG C, then hydroxy acrylic acid is added in four-hole bottle, stirs 52min, obtain Hydroxylated acrylic resin performed polymer；
(2) 3.2mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5.2, rise temperature
Then degree adds 0.45mol MethylethoxylsiliconFluid Fluids, stirring reaction 45min to 62 DEG C；
(3) 0.09mol benzoyl peroxides are first added into the reaction solution of step (2), 0.45mol is then slowly added dropwise and is modified first
Base acrylic acid trifluoro ethyl ester, stirring reaction 42min.
Wherein, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 185mL deionized waters are added into four-hole bottle, then add 0.18mol sodium alkyl benzene sulfonates and 0.1mol ammonium persulfates to lead to
Enter the air in nitrogen discharge four-hole bottle, be then stirred 40min；
(b) 0.45mol trifluoroethyl methacrylates and 0.32mol ethyl acrylates are added in the solution into step (a), is stirred
3.5h is mixed, then heats to 68 DEG C, reacts 35min, then is cooled to 36 DEG C, obtains modified methacrylic acid trifluoro ethyl ester.
Wherein, the preparation method of modified organic silicone resin comprises the following steps：
(1) 18g trim,ethylchlorosilanes and 6g ethyl chlorosilanes are added in 65mL dimethyl formamide solutions, stirred at normal temperatures
Mix 1.2 hours, then adding 6g dichloro-diethyl silanes, stirring 42 minutes, obtain chlorosilane mixed liquor；
(2) 52mL methanol and 13mL dichloromethane are added in 160mL distilled water, are warming up to 56 DEG C, then add chlorine silicon
Alkane mixed liquor, stir 2.2 hours, obtain organic-silicone prepolymer solution；
(3) 7g flyash is added in 82mL methanol solutions, it is molten then adds the organic-silicone prepolymer that step (2) obtains
Liquid, it is stirred 3.5 hours, obtains modified organic silicone resin.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred, mixing speed 145r/min, mixing time 52min；
(B) temperature of reaction kettle is increased to 72 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 130r/min, mixing time 1.2h；
(C) natural cooling after the completion of question response, for the anti-water resistance high-temperature resistance adhesive of preparation.
Embodiment 3
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：60 parts of modified hydroxyl acrylic resin,
27 parts of modified organic silicone resin, 3 parts of dimethylbenzene, 5 parts of tributyl phosphate, 2.5 parts of hydroquinones, 4 parts of polyetheramine, the second of vinyl three
20 parts of 2.5 parts of TMOS and flake asbestos.
Wherein, the preparation method of modified hydroxyl acrylic resin comprises the following steps：
(1) 116mL dioxane and 0.03mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen, be then heated to
60 DEG C, then hydroxy acrylic acid is added in four-hole bottle, stirs 55min, obtain Hydroxylated acrylic resin performed polymer；
(2) 3.5mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5.5, rise temperature
Then degree adds 0.5mol MethylethoxylsiliconFluid Fluids, stirring reaction 50min to 65 DEG C；
(3) 0.1mol benzoyl peroxides are first added into the reaction solution of step (2), 0.5mol modified methyls are then slowly added dropwise
Acrylic acid trifluoro ethyl ester, stirring reaction 45min.
Wherein, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 190mL deionized waters are added into four-hole bottle, then add 0.2mol sodium alkyl benzene sulfonates and 0.12mol ammonium persulfates to lead to
Enter the air in nitrogen discharge four-hole bottle, be then stirred 50min；
(b) 0.5mol trifluoroethyl methacrylates and 0.35mol ethyl acrylates are added in the solution into step (a), is stirred
4h is mixed, then heats to 70 DEG C, reacts 40min, then is cooled to 37 DEG C, obtains modified methacrylic acid trifluoro ethyl ester.
Wherein, the preparation method of modified organic silicone resin comprises the following steps：
(1) 20g trim,ethylchlorosilanes and 7g ethyl chlorosilanes are added in 70mL dimethyl formamide solutions, stirred at normal temperatures
Mix 1.5 hours, then adding 7g dichloro-diethyl silanes, stirring 45 minutes, obtain chlorosilane mixed liquor；
(2) 55mL methanol and 14mL dichloromethane are added in 170mL distilled water, are warming up to 57 DEG C, then add chlorine silicon
Alkane mixed liquor, stir 2.5 hours, obtain organic-silicone prepolymer solution；
(3) 8g flyash is added in 85mL methanol solutions, it is molten then adds the organic-silicone prepolymer that step (2) obtains
Liquid, it is stirred 4 hours, obtains modified organic silicone resin.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred, mixing speed 150r/min, mixing time 55min；
(B) temperature of reaction kettle is increased to 75 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 135r/min, mixing time 1.5h；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Embodiment 4
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：65 parts of modified hydroxyl acrylic resin,
28 parts of modified organic silicone resin, 4 parts of dimethylbenzene, 7 parts of tributyl phosphate, 3 parts of hydroquinones, 5 parts of polyetheramine, the ethoxy of vinyl three
21 parts of 3 parts of base silane and flake asbestos.
Wherein, the preparation method of modified hydroxyl acrylic resin comprises the following steps：
(1) 118mL dioxane and 0.04mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen, be then heated to
62 DEG C, then hydroxy acrylic acid is added in four-hole bottle, stirs 58min, obtain Hydroxylated acrylic resin performed polymer；
(2) 3.8mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5.8, rise temperature
Then degree adds 0.55mol MethylethoxylsiliconFluid Fluids, stirring reaction 55min to 68 DEG C；
(3) 0.11mol benzoyl peroxides are first added into the reaction solution of step (2), 0.55mol is then slowly added dropwise and is modified first
Base acrylic acid trifluoro ethyl ester, stirring reaction 48min.
Wherein, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 195mL deionized waters are added into four-hole bottle, then add 0.22mol sodium alkyl benzene sulfonates and 0.14mol ammonium persulfates to lead to
Enter the air in nitrogen discharge four-hole bottle, be then stirred 55min；
(b) 0.55mol trifluoroethyl methacrylates and 0.38mol ethyl acrylates are added in the solution into step (a), is stirred
4.5h is mixed, then heats to 72 DEG C, reacts 45min, then is cooled to 39 DEG C, obtains modified methacrylic acid trifluoro ethyl ester.
Wherein, the preparation method of modified organic silicone resin comprises the following steps：
(1) 22g trim,ethylchlorosilanes and 8g ethyl chlorosilanes are added in 75mL dimethyl formamide solutions, stirred at normal temperatures
Mix 1.8 hours, then adding 8g dichloro-diethyl silanes, stirring 48 minutes, obtain chlorosilane mixed liquor；
(2) 58mL methanol and 15mL dichloromethane are added in 175mL distilled water, are warming up to 58 DEG C, then add chlorine silicon
Alkane mixed liquor, stir 2.8 hours, obtain organic-silicone prepolymer solution；
(3) 9g flyash is added in 88mL methanol solutions, it is molten then adds the organic-silicone prepolymer that step (2) obtains
Liquid, it is stirred 4.5 hours, obtains modified organic silicone resin.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred, mixing speed 155r/min, mixing time 58min；
(B) temperature of reaction kettle is increased to 78 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 140r/min, mixing time 1.8h；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Embodiment 5
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：70 parts of modified hydroxyl acrylic resin,
30 parts of modified organic silicone resin, 4 parts of dimethylbenzene, 8 parts of tributyl phosphate, 4 parts of hydroquinones, 6 parts of polyetheramine, the ethoxy of vinyl three
22 parts of 4 parts of base silane and flake asbestos.
Wherein, the preparation method of modified hydroxyl acrylic resin comprises the following steps：
(1) 120mL dioxane and 0.05mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen, be then heated to
65 DEG C, then hydroxy acrylic acid is added in four-hole bottle, stirs 60min, obtain Hydroxylated acrylic resin performed polymer；
(2) 4mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 6, and rise temperature is extremely
70 DEG C, then add 0.6mol MethylethoxylsiliconFluid Fluids, stirring reaction 60min；
(3) 0.12mol benzoyl peroxides are first added into the reaction solution of step (2), 0.6mol is then slowly added dropwise and is modified first
Base acrylic acid trifluoro ethyl ester, stirring reaction 50min.
Wherein, the preparation method of the modified methacrylic acid trifluoro ethyl ester comprises the following steps：
(a) 200mL deionized waters are added into four-hole bottle, then add 0.25mol sodium alkyl benzene sulfonates and 0.15mol ammonium persulfates to lead to
Enter the air in nitrogen discharge four-hole bottle, be then stirred 60min；
(b) 0.6mol trifluoroethyl methacrylates and 0.4mol ethyl acrylates, stirring are added in the solution into step (a)
5h, 75 DEG C are then heated to, react 50min, then be cooled to 40 DEG C, obtain modified methacrylic acid trifluoro ethyl ester.
Wherein, the preparation method of modified organic silicone resin comprises the following steps：
(1) 25g trim,ethylchlorosilanes and 9g ethyl chlorosilanes are added in 80mL dimethyl formamide solutions, stirred at normal temperatures
Mix 2 hours, then adding 9g dichloro-diethyl silanes, stirring 50 minutes, obtain chlorosilane mixed liquor；
(2) 60mL methanol and 16mL dichloromethane are added in 180mL distilled water, are warming up to 60 DEG C, then add chlorine silicon
Alkane mixed liquor, stir 3 hours, obtain organic-silicone prepolymer solution；
(3) 10g flyash is added in 90mL methanol solutions, then adds the organic-silicone prepolymer that step (2) obtains
Solution, it is stirred 5 hours, obtains modified organic silicone resin.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) first add into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred, mixing speed 160r/min, mixing time 60min；
(B) temperature of reaction kettle is increased to 80 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 150r/min, mixing time 2h；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Comparative example 1
A kind of waterproof heat-resisting adhesive, the raw material matched by following parts by weight are made：It is 60 parts of Hydroxylated acrylic resin, organic
27 parts of silicones, 3 parts of dimethylbenzene, 5 parts of tributyl phosphate, 2.5 parts of hydroquinones, 4 parts of polyetheramine, VTES
2.5 parts and 20 parts of flake asbestos.
A kind of preparation method of waterproof heat-resisting adhesive, comprises the following steps：
(A) Hydroxylated acrylic resin, organic siliconresin, flake asbestos and VTES are first added into reactor,
Material is sufficiently stirred, mixing speed 150r/min, mixing time 55min；
(B) temperature of reaction kettle is increased to 75 DEG C, the dimethylbenzene of formulation weight part, tributyl phosphate, right is added into reactor
Benzenediol, polyetheramine, are then sufficiently stirred again, mixing speed 135r/min, mixing time 1.5h；
(C) natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
Embodiment 1 is gluing to embodiment 5, comparative example 1 (Hydroxylated acrylic resin and organic siliconresin be not by being modified)
Contact angle, peel strength and such as following table of agent：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Contact angle (°) | 130 | 125 | 128 | 124 | 120 | 89 |
| Peel strength (N/mm) | 12.2 | 11.4 | 11.5 | 11.7 | 12.3 | 8.1 |
As can be seen here, greatly improved by the Hydroxylated acrylic resin after modification, hydrophobicity；Can according to adhesive peel strength
Obtain, by modified organic siliconresin, the adhesive of preparation has preferable resistance to elevated temperatures.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the technical spirit pair according to the present invention without departing from technical solution of the present invention content
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (7)
1. a kind of waterproof heat-resisting adhesive, it is characterized in that, the raw material matched by following parts by weight is made：Modified hydroxyl propylene
50 ~ 70 parts of acid resin, 25 ~ 30 parts of modified organic silicone resin, 2 ~ 4 parts of dimethylbenzene, 3 ~ 8 parts of tributyl phosphate, hydroquinones 1 ~ 4
18 ~ 22 parts of part, 2 ~ 6 parts of polyetheramine, 1 ~ 4 part of VTES and flake asbestos.
2. a kind of waterproof heat-resisting adhesive according to claim 1, it is characterized in that, the modified hydroxyl acrylic resin
Preparation method comprise the following steps：
（1）110 ~ 120mL dioxane and 0.02 ~ 0.05mol azodiisobutyronitriles are added in four-hole bottle, pour nitrogen,
55 ~ 65 DEG C are then heated to, then hydroxy acrylic acid is added in four-hole bottle, 50 ~ 60min is stirred, obtains hydroxy acrylic acid
Resin prepolymer；
（2）3 ~ 4mol/L watery hydrochloric acid solvent is slowly dropped in hydroxy acrylic acid performed polymer, regulation pH is 5 ~ 6, rise temperature
Then degree adds 0.4 ~ 0.6mol MethylethoxylsiliconFluid Fluids, 40 ~ 60min of stirring reaction to 60 ~ 70 DEG C；
（3）To step（2）Reaction solution in first add 0.08 ~ 0.12mol benzoyl peroxides, be then slowly added dropwise 0.4 ~
0.6mol modified methacrylic acid trifluoro ethyl esters, 40 ~ 50min of stirring reaction.
3. a kind of waterproof heat-resisting adhesive according to claim 2, it is characterized in that, the modified methacrylic acid trifluoro
The preparation method of ethyl ester comprises the following steps：
（a）180 ~ 200mL deionized waters are added into four-hole bottle, then add 0.15 ~ 0.25mol sodium alkyl benzene sulfonates and 0.8 ~
0.15mol ammonium persulfates are passed through the air in nitrogen discharge four-hole bottle, are then stirred 30 ~ 60min；
（b）To step（a）In solution in add 0.4 ~ 0.6mol trifluoroethyl methacrylates and 0.3 ~ 0.4mol acrylic acid
Ethyl ester, 3 ~ 5h is stirred, then heat to 65 ~ 75 DEG C, react 30 ~ 50min, then be cooled to 35 ~ 40 DEG C, obtain modified methyl propylene
Sour trifluoro ethyl ester.
4. a kind of waterproof heat-resisting adhesive according to claim 1, it is characterized in that, the system of the modified organic silicone resin
Preparation Method comprises the following steps：
（1）15 ~ 25g trim,ethylchlorosilanes and 5 ~ 9g ethyl chlorosilanes are added in 60 ~ 80 mL dimethyl formamide solutions,
Stir at normal temperatures 1 ~ 2 hour, then adding 5 ~ 9g dichloro-diethyl silanes, stirring 40 ~ 50 minutes, obtain chlorosilane mixing
Liquid；
（2）50 ~ 60 mL methanol and 12 ~ 16mL dichloromethane are added in 150 ~ 180mL distilled water, are warming up to 55 ~ 60
DEG C, chlorosilane mixed liquor is then added, stirs 2 ~ 3 hours, obtains organic-silicone prepolymer solution；
（3）6 ~ 10g flyash is added in 80 ~ 90mL methanol solutions, then adds step（2）Obtained organic siliconresin is pre-
Oligomer solution, it is stirred 3 ~ 5 hours, obtains modified organic silicone resin.
5. a kind of preparation method of waterproof heat-resisting adhesive as described in claim 1 ~ 4 any claim, it is characterized in that,
Comprise the following steps：
（A）First added into reactor the modified hydroxyl acrylic resin of formulation weight part, modified organic silicone resin, flake asbestos and
VTES, material is sufficiently stirred；
（B）Temperature of reaction kettle is increased to 70 ~ 80 DEG C, added into reactor the dimethylbenzene of formulation weight part, tributyl phosphate,
Hydroquinones, polyetheramine, are then sufficiently stirred again；
（C）Natural cooling after the completion of question response, for the waterproof heat-resisting adhesive of preparation.
6. a kind of preparation method of waterproof heat-resisting adhesive according to claim 5, it is characterized in that, the step（A）
Middle mixing speed is 140 ~ 160r/min, and mixing time is 50 ~ 60min.
7. a kind of preparation method of waterproof heat-resisting adhesive according to claim 5, it is characterized in that, the step（B）
Middle mixing speed is 120 ~ 150 r/min, and mixing time is 1 ~ 2h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330925A (en) * | 2019-06-04 | 2019-10-15 | 中电鼎康（天长）科技有限公司 | A kind of sensor potent moisture-proof adhesive and preparation method thereof |
| CN111676078A (en) * | 2020-06-22 | 2020-09-18 | 郑翔书 | Coal powder and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773257A (en) * | 2014-01-20 | 2014-05-07 | 南通耀华机电有限公司 | Adhesive film for encapsulating electronic element |
| CN104789184A (en) * | 2015-03-31 | 2015-07-22 | 苏州市鼎立包装有限公司 | High-temperature-resistant and anti-aging bonder and preparation method thereof |
| CN106010353A (en) * | 2016-05-30 | 2016-10-12 | 成都市惠家胶粘制品有限公司 | High temperature resistant crepe paper adhesive tape |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773257A (en) * | 2014-01-20 | 2014-05-07 | 南通耀华机电有限公司 | Adhesive film for encapsulating electronic element |
| CN104789184A (en) * | 2015-03-31 | 2015-07-22 | 苏州市鼎立包装有限公司 | High-temperature-resistant and anti-aging bonder and preparation method thereof |
| CN106010353A (en) * | 2016-05-30 | 2016-10-12 | 成都市惠家胶粘制品有限公司 | High temperature resistant crepe paper adhesive tape |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330925A (en) * | 2019-06-04 | 2019-10-15 | 中电鼎康（天长）科技有限公司 | A kind of sensor potent moisture-proof adhesive and preparation method thereof |
| CN111676078A (en) * | 2020-06-22 | 2020-09-18 | 郑翔书 | Coal powder and preparation process thereof |
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