CN103173114B - 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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- CN103173114B CN103173114B CN201310096125.4A CN201310096125A CN103173114B CN 103173114 B CN103173114 B CN 103173114B CN 201310096125 A CN201310096125 A CN 201310096125A CN 103173114 B CN103173114 B CN 103173114B
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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 preparing this epoxy modified silicone resin sizing agent.
Background technology
Sizing agent refers to sticking and interiorly poly-ly waiting effect by interface, and the natural or synthesis that two or more product or material can be made to link together, an organic or inorganic class 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 by the material sticking thing and combine; Tradition sizing agent due to formulation ratio unreasonable, its cementability is poor, can not meet user demand.
Summary of the invention
The object of the invention is in order to overcome weak point of the prior art, to provide a kind of component and reasonable ratio, the epoxy modified silicone resin sizing agent that adhesiveproperties is good.
Another object of the present invention is to provide a kind of method 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 is by 80 weight part hydroxyl endblocked polydimethylsiloxanes, 30 parts by weight of bisphenol A type epoxy resin 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, diethylamine 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 modified dicyandiamine and imidazoles are by weight the mixture for 5:2.
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 preparing epoxy modified silicone resin sizing agent described above of the present invention, is characterized in that comprising the following steps:
A, prepare polyurethane modified epoxy resin
Polyester polyol is heated to 100-120 DEG C of reflux dewatering, be cooled to 40-60 DEG C, add diphenylmethanediisocyanate, be heated to 65-80 DEG C, reaction 1-3 hour, is cooled to room temperature, adds 2,3 butyleneglycols and TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, epoxy resin is joined in base polyurethane prepolymer for use as and react 1-3 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
Bisphenol fluorene, epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50-60 DEG C, stir 45-90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.05-0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add ethanamide reaction 1-3 hour, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Epoxy modified silicone resin sizing agent cementability of the present invention is good, and technique is simple, and the materials such as metal, glass, plastic ceramic have good cementability.
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:
Preparation method:
A, prepare polyurethane modified epoxy resin
15 weight of polyester polyvalent alcohols are heated to 100 DEG C of reflux dewaterings, be cooled to 40 DEG C, add 4 weight part diphenylmethanediisocyanates, be heated to 65 DEG C, react 1 hour, be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 1 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
10 parts by weight of bisphenol fluorenes, 30 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 0.5 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50 DEG C, stir 45min, reactor is vacuumized, to make in reactor vacuum degree control at 0.05MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8 weight part ethanamides and react 1 hour, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 2
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
20 weight of polyester polyvalent alcohols are heated to 120 DEG C of reflux dewaterings, be cooled to 60 DEG C, add 7 weight part diphenylmethanediisocyanates, be heated to 80 DEG C, react 3 hours, be cooled to room temperature, add 2 weight parts 2,3 butyleneglycols and 3 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 3 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
20 parts by weight of bisphenol fluorenes, 100 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1.5 weight part benzyltriethylammoinium chlorides and appropriate Strong oxdiative sodium solution after abundant dissolving, at 60 DEG C, stir 90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 40 weight part ethanamides and react 3 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 3
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
16 weight of polyester polyvalent alcohols are heated to 110 DEG C of reflux dewaterings, be cooled to 50 DEG C, add 5 weight part diphenylmethanediisocyanates, be heated to 70 DEG C, react 2 hours, be cooled to room temperature, add 1 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 2 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
15 parts by weight of bisphenol fluorenes, 50 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 55 DEG C, stir 60min, reactor is vacuumized, to make in reactor vacuum degree control 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;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 4
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
17 weight of polyester polyvalent alcohols are heated to 115 DEG C of reflux dewaterings, be cooled to 55 DEG C, add 6 weight part diphenylmethanediisocyanates, be heated to 75 DEG C, react 1 hour, be cooled to room temperature, add 1.5 weight parts 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 2 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
12 parts by weight of bisphenol fluorenes, 40 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 0.8 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 58 DEG C, stir 65min, reactor is vacuumized, to make in reactor vacuum degree control at 0.06MPa, drip appropriate sodium hydroxide solution under vacuum state, add 10 weight part ethanamides and react 2 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 5
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
18 weight of polyester polyvalent alcohols are heated to 105 DEG C of reflux dewaterings, be cooled to 45 DEG C, add 4 weight part diphenylmethanediisocyanates, be heated to 70 DEG C, react 3 hours, be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 1 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
18 parts by weight of bisphenol fluorenes, 80 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1.2 weight part benzyltriethylammoinium chlorides and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50 DEG C, stir 90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 30 weight part ethanamides and react 2 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 6
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
15 weight of polyester polyvalent alcohols are heated to 100 DEG C of reflux dewaterings, be cooled to 40 DEG C, add 4 weight part diphenylmethanediisocyanates, be heated to 65 DEG C, react 1 hour, be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 1 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
10 parts by weight of bisphenol fluorenes, 30 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 0.5 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50 DEG C, stir 45min, reactor is vacuumized, to make in reactor vacuum degree control at 0.05MPa, drip appropriate sodium hydroxide solution under vacuum state, add 8 weight part ethanamides and react 1 hour, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 7
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
20 weight of polyester polyvalent alcohols are heated to 120 DEG C of reflux dewaterings, be cooled to 60 DEG C, add 7 weight part diphenylmethanediisocyanates, be heated to 80 DEG C, react 3 hours, be cooled to room temperature, add 2 weight parts 2,3 butyleneglycols and 3 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 3 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
20 parts by weight of bisphenol fluorenes, 100 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1.5 weight part benzyltriethylammoinium chlorides and appropriate Strong oxdiative sodium solution after abundant dissolving, at 60 DEG C, stir 90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 40 weight part ethanamides and react 3 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 8
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
16 weight of polyester polyvalent alcohols are heated to 110 DEG C of reflux dewaterings, be cooled to 50 DEG C, add 5 weight part diphenylmethanediisocyanates, be heated to 70 DEG C, react 2 hours, be cooled to room temperature, add 1 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 2 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
15 parts by weight of bisphenol fluorenes, 50 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 55 DEG C, stir 60min, reactor is vacuumized, to make in reactor vacuum degree control 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;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 9
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
17 weight of polyester polyvalent alcohols are heated to 115 DEG C of reflux dewaterings, be cooled to 55 DEG C, add 6 weight part diphenylmethanediisocyanates, be heated to 75 DEG C, react 1 hour, be cooled to room temperature, add 1.5 weight parts 2,3 butyleneglycols and 1 weight part TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 2 hours, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
12 parts by weight of bisphenol fluorenes, 40 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 0.8 weight part benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 58 DEG C, stir 65min, reactor is vacuumized, to make in reactor vacuum degree control at 0.06MPa, drip appropriate sodium hydroxide solution under vacuum state, add 10 weight part ethanamides and react 2 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Embodiment 10
Epoxy modified silicone resin sizing agent of the present invention, composed of the following components by weight:
Preparation method:
A, prepare polyurethane modified epoxy resin
18 weight of polyester polyvalent alcohols are heated to 105 DEG C of reflux dewaterings, be cooled to 45 DEG C, add 4 weight part diphenylmethanediisocyanates, be heated to 70 DEG C, react 3 hours, be cooled to room temperature, add 0.5 weight part 2,3 butyleneglycols and 2 weight part TriMethylolPropane(TMP)s stir, obtain base polyurethane prepolymer for use as, 100 parts by weight epoxy resin are joined in base polyurethane prepolymer for use as and react 1 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 170 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5kPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
18 parts by weight of bisphenol fluorenes, 80 parts by weight epoxy chloropropanes are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add 1.2 weight part benzyltriethylammoinium chlorides and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50 DEG C, stir 90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add 30 weight part ethanamides and react 2 hours, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
Claims (8)
1. an epoxy modified silicone resin sizing agent, is characterized in that composed of the following components by weight:
Wherein said polyurethane modified epoxy resin is composed of the following components by weight:
2. a kind of epoxy modified silicone resin sizing agent according to claim 1, it is characterized in that described epoxy modified silicone resin is by 80 weight part hydroxyl endblocked polydimethylsiloxanes, 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates are made.
3. a kind of epoxy modified silicone resin sizing agent according to claim 2, is characterized in that described fluorenyl epoxy resin comprises following component by weight:
4. 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, diethylamine propylamine, beta-hydroxyethyl quadrol.
5. 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.
6. a kind of epoxy modified silicone resin sizing agent according to claim 1, is characterized in that described compound accelerant is that modified dicyandiamine and imidazoles are by weight the mixture for 5:2.
7. 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.
8. prepare a method for the arbitrary described epoxy modified silicone resin sizing agent of claim 1 to 7, it is characterized in that comprising the following steps:
A, prepare polyurethane modified epoxy resin
Polyester polyol is heated to 100-120 DEG C of reflux dewatering, be cooled to 40-60 DEG C, add diphenylmethanediisocyanate, be heated to 65-80 DEG C, reaction 1-3 hour, is cooled to room temperature, adds 2,3 butyleneglycols and TriMethylolPropane(TMP) stir, obtain base polyurethane prepolymer for use as, epoxy resin is joined in base polyurethane prepolymer for use as and react 1-3 hour, obtain polyurethane modified epoxy resin;
B, prepare epoxy modified silicone resin:
In a kettle., add 80 weight part hydroxyl endblocked polydimethylsiloxane 30 parts by weight of bisphenol A type epoxy resin and 3 weight part dibutyl tin dilaurates, under stirring, be warming up to 70 DEG C, maintain 30 minutes; Be warming up to 110 DEG C, react 6 hours, then reaction system is warming up to 160 DEG C, maintain 30 minutes, at 180 DEG C, deviate from low-boiling-point substance under 1.5KPa 1 hour, obtain epoxy modified silicone resin;
C, prepare fluorenyl epoxy resin
Bisphenol fluorene, epoxy chloropropane are added in reactor, under nitrogen protection, be warming up to 45 DEG C, add benzyltriethylammoinium chloride and appropriate Strong oxdiative sodium solution after abundant dissolving, at 50-60 DEG C, stir 45-90min, reactor is vacuumized, to make in reactor vacuum degree control at 0.05-0.1MPa, drip appropriate sodium hydroxide solution under vacuum state, add ethanamide reaction 1-3 hour, be washed to pH=7;
D, prepare epoxy modified silicone resin sizing agent
Take each component in proportion, polyurethane modified epoxy resin, epoxy modified silicone resin, fluorenyl epoxy resin, carboxy terminated polybutadiene vinyl cyanide fluid rubber, be uniformly mixed at 50-70 DEG C; Add solidifying agent, thixotropic agent, coupling agent, be heated to 70-90 DEG C, stir, after vacuum defoamation, be cooled to room temperature, stir at 40-50 DEG C and add compound accelerant to mixing.
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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 |
| CN105754071A (en) * | 2016-02-29 | 2016-07-13 | 宏昌电子材料股份有限公司 | Preparation technology of bisphenol fluorene epoxy resin |
| CN107527984B (en) * | 2016-06-22 | 2019-10-18 | 惠州雷通光电器件有限公司 | Silicon resin glue and its application method in LED encapsulation |
| CN108034352B (en) * | 2017-12-27 | 2020-02-07 | 科顺防水科技股份有限公司 | Primer for modified silicone sealant suitable for PC (polycarbonate) building and preparation method of primer |
| 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 |
| CN110791196B (en) * | 2019-11-15 | 2021-03-09 | 江南大学 | Preparation method of photo-thermal dual-curing high-weather-resistance organic silicon modified epoxy resin |
| CN113621230B (en) * | 2021-09-01 | 2022-07-15 | 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 |
| 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 |
| CN116180451A (en) * | 2023-03-01 | 2023-05-30 | 湖南泽睿新材料有限公司 | Continuous silicon carbide fiber sizing agent and application 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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