CN103173114A - Epoxy modified organic silicon resin adhesive and preparation method thereof - Google Patents
Epoxy modified organic silicon resin adhesive and preparation method thereof Download PDFInfo
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- CN103173114A CN103173114A CN2013100961254A CN201310096125A CN103173114A CN 103173114 A CN103173114 A CN 103173114A CN 2013100961254 A CN2013100961254 A CN 2013100961254A CN 201310096125 A CN201310096125 A CN 201310096125A CN 103173114 A CN103173114 A CN 103173114A
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Abstract
The invention discloses an epoxy modified organic silicon resin adhesive and a preparation method thereof. The adhesive is prepared from the following components of 10-30 parts of polyurethane modified epoxy resin, 20-70 parts of epoxy modified organic silicon resin, 20-60 parts of fluorene-based epoxy resin, 10-40 parts of carboxyl-polybutadiene acrylonitrile liquid rubber, 10-60 parts of curing agent, 1-8 parts of thixotropic agent, 0.5-3 parts of compound accelerator and 2-6 parts of coupling agent. The preparation method comprises the steps of weighing each component according to the ratio, evenly mixing the polyurethane modified epoxy resin, the epoxy modified organic silicon resin, the fluorene-based epoxy resin and the carboxyl-polybutadiene acrylonitrile liquid rubber under agitation at 50-70 DEG C; adding the curing agent, the thixotropic agent and the coupling agent and heating to 70-90 DEG C; evenly agitating, and cooling to room temperature after vacuum defoaming; and adding the compound accelerator under agitation at 40-50 DEG C until evenly mixing. The modified epoxy resin adhesive is good in adhesion and simple in process, and has good adhesion on materials such as metal, glass, and plastic ceramic.
Description
Technical field
The present invention relates to a kind of epoxy modified silicone resin sizing agent; The invention still further relates to a kind of method for preparing this epoxy modified silicone resin sizing agent.
Background technology
Sizing agent refers to by the sticking and the interior poly-effect that waits of interface, and can make two or more product or natural or synthetic, the organic or inorganic class material that links together of material, is referred to as sizing agent, is again tamanori, traditionally referred to as glue.In brief, sizing agent is exactly by adhesive effect, can make the material that is combined by glutinous thing; The tradition sizing agent is because formulation ratio is unreasonable, and its cementability is relatively poor, can not satisfy user demand.
Summary of the invention
The objective of the invention is provides a kind of component and reasonable ratio in order to overcome weak point of the prior art, the epoxy modified silicone resin sizing agent that adhesiveproperties is good.
Another object of the present invention is to provide a kind of method for preparing this epoxy modified silicone resin sizing agent.
In order to achieve the above object, the present invention adopts following scheme:
A kind of epoxy modified silicone resin sizing agent is characterized in that composed of the following components by weight:
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described polyurethane modified epoxy resin is composed of the following components by weight:
A kind of epoxy modified silicone resin sizing agent as above, it is characterized in that described epoxy modified silicone resin by 80 weight part hydroxyl endblocked polydimethylsiloxanes, 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates are made.
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described fluorenyl epoxy resin comprises following component by weight:
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described solidifying agent is one or more the mixing in dimethyl amine propylamine, diethylamide propylamine, beta-hydroxyethyl quadrol.
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described thixotropic agent is one or more the mixture in aerosil, organobentonite, hydrogenated castor oil.
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described compound accelerant is that modification Dyhard RU 100 and imidazoles are the mixture of 5:2 by weight.
A kind of epoxy modified silicone resin sizing agent as above is characterized in that described coupling agent is one or more the mixture in Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH792.
A kind of method of epoxy modified silicone resin sizing agent as mentioned above for preparing of the present invention is characterized in that comprising the following steps:
A, preparation polyurethane modified epoxy resin
Polyester polyol is heated to 100-120 ℃ of reflux dewatering, be cooled to 40-60 ℃, add diphenylmethanediisocyanate, be heated to 65-80 ℃, reaction 1-3 hour is cooled to room temperature, adds 2,3 butyleneglycols and TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, epoxy resin is joined react 1-3 hour in base polyurethane prepolymer for use as, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
Bisphenol fluorene, epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 45-90min under 50-60 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.05-0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add ethanamide reaction 1-3 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Epoxy modified silicone resin sizing agent cementability of the present invention is good, and technique is simple, on the materials such as metal, glass, plastics pottery, good cementability is arranged.
Embodiment
Below in conjunction with embodiment, the present invention is described further:
Embodiment 1
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
15 weight part polyester polyols are heated to 100 ℃ of reflux dewaterings, be cooled to 40 ℃, add 4 weight part diphenylmethanediisocyanates, be heated to 65 ℃, reacted 1 hour, and be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 1 hour, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
10 weight part bisphenol fluorenes, 30 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 0.5 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 45min under 50 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.05MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8 weight part ethanamide reaction 1 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 2
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
20 weight part polyester polyols are heated to 120 ℃ of reflux dewaterings, be cooled to 60 ℃, add 7 weight part diphenylmethanediisocyanates, be heated to 80 ℃, reacted 3 hours, and be cooled to room temperature, add 2 weight parts 2,3 butyleneglycols and 3 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 3 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
20 weight part bisphenol fluorenes, 100 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1.5 weight part benzyltriethylammoinium chlorides and appropriate strong sodium hydroxide solution after dissolving, stir 90min under 60 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 40 weight part ethanamide reaction 3 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 3
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
16 weight part polyester polyols are heated to 110 ℃ of reflux dewaterings, be cooled to 50 ℃, add 5 weight part diphenylmethanediisocyanates, be heated to 70 ℃, reacted 2 hours, and be cooled to room temperature, add 1 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 2 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
15 weight part bisphenol fluorenes, 50 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 60min under 55 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.08MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8-40 weight part ethanamide reaction 1-3 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 4
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
17 weight part polyester polyols are heated to 115 ℃ of reflux dewaterings, be cooled to 55 ℃, add 6 weight part diphenylmethanediisocyanates, be heated to 75 ℃, reacted 1 hour, and be cooled to room temperature, add 1.5 weight parts 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 2 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
12 weight part bisphenol fluorenes, 40 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 0.8 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 65min under 58 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.06MPa, drip appropriate sodium hydroxide solution under vacuum state, add 10 weight part ethanamide reaction 2 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 5
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
18 weight part polyester polyols are heated to 105 ℃ of reflux dewaterings, be cooled to 45 ℃, add 4 weight part diphenylmethanediisocyanates, be heated to 70 ℃, reacted 3 hours, and be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 1 hour, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
18 weight part bisphenol fluorenes, 80 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1.2 weight part benzyltriethylammoinium chlorides and appropriate strong sodium hydroxide solution after dissolving, stir 90min under 50 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 30 weight part ethanamide reaction 2 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 6
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
15 weight part polyester polyols are heated to 100 ℃ of reflux dewaterings, be cooled to 40 ℃, add 4 weight part diphenylmethanediisocyanates, be heated to 65 ℃, reacted 1 hour, and be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 1 hour, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
10 weight part bisphenol fluorenes, 30 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 0.5 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 45min under 50 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.05MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8 weight part ethanamide reaction 1 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 7
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
20 weight part polyester polyols are heated to 120 ℃ of reflux dewaterings, be cooled to 60 ℃, add 7 weight part diphenylmethanediisocyanates, be heated to 80 ℃, reacted 3 hours, and be cooled to room temperature, add 2 weight parts 2,3 butyleneglycols and 3 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 3 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
20 weight part bisphenol fluorenes, 100 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1.5 weight part benzyltriethylammoinium chlorides and appropriate strong sodium hydroxide solution after dissolving, stir 90min under 60 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 40 weight part ethanamide reaction 3 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 8
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
16 weight part polyester polyols are heated to 110 ℃ of reflux dewaterings, be cooled to 50 ℃, add 5 weight part diphenylmethanediisocyanates, be heated to 70 ℃, reacted 2 hours, and be cooled to room temperature, add 1 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 2 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
15 weight part bisphenol fluorenes, 50 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 60min under 55 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.08MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8-40 weight part ethanamide reaction 1-3 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 9
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
17 weight part polyester polyols are heated to 115 ℃ of reflux dewaterings, be cooled to 55 ℃, add 6 weight part diphenylmethanediisocyanates, be heated to 75 ℃, reacted 1 hour, and be cooled to room temperature, add 1.5 weight parts 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 2 hours, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
12 weight part bisphenol fluorenes, 40 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 0.8 weight part benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 65min under 58 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.06MPa, drip appropriate sodium hydroxide solution under vacuum state, add 10 weight part ethanamide reaction 2 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Embodiment 10
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
The preparation method:
A, preparation polyurethane modified epoxy resin
18 weight part polyester polyols are heated to 105 ℃ of reflux dewaterings, be cooled to 45 ℃, add 4 weight part diphenylmethanediisocyanates, be heated to 70 ℃, reacted 3 hours, and be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, get base polyurethane prepolymer for use as, 100 weight part epoxy resin are joined in base polyurethane prepolymer for use as reacted 1 hour, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 170 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
18 weight part bisphenol fluorenes, 80 weight part epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add 1.2 weight part benzyltriethylammoinium chlorides and appropriate strong sodium hydroxide solution after dissolving, stir 90min under 50 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 30 weight part ethanamide reaction 2 hours, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
Claims (9)
1. epoxy modified silicone resin sizing agent is characterized in that composed of the following components by weight:
2. a kind of epoxy modified silicone resin sizing agent according to claim 1 is characterized in that described polyurethane modified epoxy resin is composed of the following components by weight:
3. a kind of epoxy modified silicone resin sizing agent according to claim 2, it is characterized in that described epoxy modified silicone resin by 80 weight part hydroxyl endblocked polydimethylsiloxanes, 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates are made.
4. a kind of epoxy modified silicone resin sizing agent according to claim 3 is characterized in that described fluorenyl epoxy resin comprises following component by weight:
5. a kind of epoxy modified silicone resin sizing agent according to claim 1 is characterized in that described solidifying agent is one or more the mixing in dimethyl amine propylamine, diethylamide propylamine, beta-hydroxyethyl quadrol.
6. a kind of epoxy modified silicone resin sizing agent according to claim 1 is characterized in that described thixotropic agent is one or more the mixture in aerosil, organobentonite, hydrogenated castor oil.
7. a kind of epoxy modified silicone resin sizing agent according to claim 1, is characterized in that described compound accelerant is that modification Dyhard RU 100 and imidazoles are the mixture of 5:2 by weight.
8. a kind of epoxy modified silicone resin sizing agent according to claim 1 is characterized in that described coupling agent is one or more the mixture in Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH792.
9. method for preparing the described arbitrary epoxy modified silicone resin sizing agent of claim 1 to 8 is characterized in that comprising the following steps:
A, preparation polyurethane modified epoxy resin
Polyester polyol is heated to 100-120 ℃ of reflux dewatering, be cooled to 40-60 ℃, add diphenylmethanediisocyanate, be heated to 65-80 ℃, reaction 1-3 hour is cooled to room temperature, adds 2,3 butyleneglycols and TriMethylolPropane(TMP) stir, get base polyurethane prepolymer for use as, epoxy resin is joined react 1-3 hour in base polyurethane prepolymer for use as, get polyurethane modified epoxy resin;
B, preparation epoxy modified silicone resin:
In reactor, add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 weight part bisphenol A type epoxy resins and 3 weight part dibutyl tin dilaurates, be warming up to 70 ℃ under stirring, kept 30 minutes; Be warming up to 110 ℃, reacted 6 hours, then reaction system is warming up to 160 ℃, kept 30 minutes, at 180 ℃, deviate from low-boiling-point substance under 1.5kPa 1 hour, namely get epoxy modified silicone resin;
C, preparation fluorenyl epoxy resin
Bisphenol fluorene, epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 ℃, fully add benzyltriethylammoinium chloride and appropriate strong sodium hydroxide solution after dissolving, stir 45-90min under 50-60 ℃, reactor is vacuumized, make the interior vacuum degree control of reactor at 0.05-0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add ethanamide reaction 1-3 hour, be washed to pH=7 and get final product;
D, preparation epoxy modified silicone resin sizing agent
Take in proportion each component, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber mix under 50-70 ℃; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 ℃, stir, be cooled to room temperature after vacuum defoamation, stirring adds compound accelerant to mixing under 40-50 ℃, gets final product.
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| CN104531034A (en) * | 2014-10-09 | 2015-04-22 | 广东新展化工新材料有限公司 | Polyurethane-modified epoxy resin adhesive and preparation method thereof |
| CN104987673A (en) * | 2015-08-05 | 2015-10-21 | 张家港康得新光电材料有限公司 | Epoxy resin composition for prepreg, carbon fiber prepreg and carbon fiber compound material |
| CN105176480A (en) * | 2015-08-19 | 2015-12-23 | 合肥市田源精铸有限公司 | Quick-drying metal-to-metal adhesive |
| WO2017147940A1 (en) * | 2016-02-29 | 2017-09-08 | 宏昌电子材料股份有限公司 | Preparation process for 4,4'-(9-fluorenylidene)diphenol epoxy resin |
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| CN104531034A (en) * | 2014-10-09 | 2015-04-22 | 广东新展化工新材料有限公司 | Polyurethane-modified epoxy resin adhesive and preparation method thereof |
| CN104987673A (en) * | 2015-08-05 | 2015-10-21 | 张家港康得新光电材料有限公司 | Epoxy resin composition for prepreg, carbon fiber prepreg and carbon fiber compound material |
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| CN108034352A (en) * | 2017-12-27 | 2018-05-15 | 科顺防水科技股份有限公司 | Modified silicone seal gum silane coupling agent suitable for PC buildings and preparation method thereof |
| CN108359365A (en) * | 2018-02-10 | 2018-08-03 | 朱东洋 | A kind of preparation method of metal repairing agent |
| CN109370494A (en) * | 2018-09-30 | 2019-02-22 | 句容峰岭科技有限公司 | A kind of adhesive and preparation method thereof of hardware plastic processing |
| CN110791196A (en) * | 2019-11-15 | 2020-02-14 | 江南大学 | Preparation method of photo-thermal dual-curing high-weather-resistance organic silicon modified epoxy resin |
| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
| CN115595089A (en) * | 2022-10-09 | 2023-01-13 | 北京康美特科技股份有限公司（Cn） | Conductive silver adhesive and preparation method and application thereof |
| CN115612402A (en) * | 2022-11-05 | 2023-01-17 | 郑州瑞特高温陶瓷有限公司 | Graphite high-temperature anticorrosive paint and preparation method thereof |
| CN115612402B (en) * | 2022-11-05 | 2023-10-24 | 郑州瑞特高温陶瓷有限公司 | Graphite high-temperature anticorrosive paint and preparation method thereof |
| CN116162441A (en) * | 2023-03-29 | 2023-05-26 | 广州宝捷电子材料科技有限公司 | Composite modified epoxy resin adhesive and preparation method thereof |
| CN116162441B (en) * | 2023-03-29 | 2023-09-19 | 广州宝捷电子材料科技有限公司 | Composite modified epoxy resin adhesive and preparation method thereof |
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