CN105061728B - Modifying method of solid epoxy resin - Google Patents
Modifying method of solid epoxy resin Download PDFInfo
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- CN105061728B CN105061728B CN201510468955.4A CN201510468955A CN105061728B CN 105061728 B CN105061728 B CN 105061728B CN 201510468955 A CN201510468955 A CN 201510468955A CN 105061728 B CN105061728 B CN 105061728B
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Abstract
The invention discloses a modifying method of solid epoxy resin, and especially relates to a modifying method for reducing the viscosity of the solid epoxy resin. The method comprises the following steps: carrying out mixing melting on base resin and bisphenol A under an oxygen isolation condition to obtain a molten material, adding a catalyst and a compound additive containing a phenolic hydroxyl group, and reacting to obtain modified solid epoxy resin. The modifying method reduces the viscosity of the epoxy resin, and widens the viscosity range of the epoxy resin under a fixed epoxy equivalent condition in order to enlarge the application range of the epoxy resin.
Description
Technical field
The present invention relates to epoxy resin modification field, more particularly to a kind of modified side for reducing solid epoxy viscosity
Method.
Background technology
Solid epoxy is the mixture of the bisphenol A diglycidyl ether of different polymerization degree, containing a certain amount of end
The component (the non-epoxide group component of end group) of non-closed loop.Solid epoxy has many premium properties, and processing technology is good, plus
Enter to have after curing agent the cohesive of height, good stability, strong compared with low water absorbable, excellent electrical insulation capability and higher machinery
Degree excellent properties.It is widely used in the fields such as electronics, electrical equipment, paint, coating, bonding, building.
The viscosity of solid epoxy is generally represented that same substance motion is viscous by the viscosity under kinematic viscosity or molten condition
Degree is one-to-one with viscosity under molten condition.In some applications to the levelability under solid epoxy molten condition
There are certain requirements, such as anticorrosive paint requires that coating possesses good levelability, and the lower levelability of epoxy resin viscosity
Better, solidification institute film forming is more smooth, and orange peel effect is fewer.So reducing the viscosity of solid epoxy can increase solid
The levelability of epoxy resin, expands range of application.
In the case of preparation technology and raw material are specific, epoxide equivalent is corresponding with kinematic viscosity to solid epoxy
, epoxide equivalent is the quality containing 1mol epoxy resin, and epoxide number be the total contained epoxy of every 100g resins material
Amount, the epoxy resin application of different epoxide equivalents is different.Under the conditions of specific epoxide equivalent, viscosity is that have certain scope
, limit the range of application of solid epoxy.Such as No. 1 solid epoxy of commercially available product：Epoxide number is 2000-
2220mmol/kg, kinematic viscosity is 6.3-7.9m2/ s, epoxide number is 2000-2220mmol/kg, is transported in the case of not being modified
The lower limit of kinetic viscosity is 6.3m2/s。
The content of the invention
It is an object of the invention to provide a kind of method of modifying of solid epoxy, the method for modifying energy that the present invention is provided
Enough reduce the viscosity of epoxy resin, under the conditions of widening fixed epoxide equivalent, the range of viscosities of epoxy resin.
The invention provides a kind of method of modifying of solid epoxy, comprises the following steps：
(1) under the conditions of starvation, by base resin and bisphenol-A mixed melting, fused materials are obtained；
(2) fused materials that the step (1) is obtained are mixed with additive and catalyst, being warming up to reaction final temperature is carried out
Reaction, obtains modified solid epoxy resin, and the additive is the compound containing phenolic hydroxyl group.
Preferably, the additive includes one or more in phenol and phenol derivatives.
Preferably, the additive includes one or more in p-t-butyl phenol, phenol and p-methyl phenol.
Preferably, the addition of the additive accounts for the ratio of base resin, bisphenol-A, additive and catalyst gross mass
No more than 5%.
Preferably, the catalyst includes one or more in triphenylphosphine and triphenylphosphine derivates.
Preferably, the catalyst includes triphenylphosphine, ethyltriphenyl phosphonium chloride phosphine, ethyltriphenylphosphonium bromide, ethyl
Triphenyl phosphonium iodide phosphine, ethyl triphenyl acetic acid phosphine and tetraphenylphosphonibromide bromide one or more.
Preferably, the addition of the catalyst account for base resin, bisphenol-A, additive and catalyst gross mass 2 ‰～
5‰。
Preferably, the programming rate in the step (2) is 1～5 DEG C/min, preferably 1 DEG C/min.
Preferably, the reaction final temperature in the step (2) is 160 DEG C～180 DEG C；
The temperature retention time of reaction is 60min～120min in the step (2).
Preferably, the temperature of melting is 110 DEG C～130 DEG C in the step (1).
The invention provides reducing the method for modifying of solid epoxy viscosity under the conditions of a kind of corresponding epoxide equivalent.Including
Following steps：(1) under the conditions of starvation, by base resin and bisphenol-A mixed melting, fused materials are obtained；(2) will be described
The fused materials that step (1) is obtained mix with additive and catalyst, are warming up to reaction final temperature and are reacted, and obtain modified solid
Epoxy resin, the additive is the compound containing phenolic hydroxyl group.The method that the present invention is provided is by the chemical combination containing phenolic hydroxyl group
The addition of thing, increases the content of the non-epoxide group in epoxy resin end, can't affect the anti-of hydroxyl on epoxy molecule chain
Ying Xing, on the bridging property after application solidification impact is had no, while also not interfering with epoxy resin overall physics, chemically stable
Property.Under the conditions of certain epoxide equivalent, reduced by adding the kinematic viscosity lower limit of additive, epoxy resin, range of viscosities
Extension, breaks through the lower viscosity limit of the conventional production of solid epoxy.Simultaneously with the reduction of epoxide number, kinematic viscosity is with addition
The addition change of agent is more obvious.
Specific embodiment
The invention provides a kind of method of modifying of solid epoxy, comprises the following steps：
(1) under the conditions of starvation, by base resin and bisphenol-A mixed melting, fused materials are obtained；
(2) fused materials that the step (1) is obtained are mixed with additive and catalyst, being warming up to reaction final temperature is carried out
Reaction, obtains modified solid epoxy resin, and the additive is the compound containing phenolic hydroxyl group.
The method that the present invention is provided, can reduce the viscosity of the solid epoxy under the conditions of corresponding epoxide equivalent.
Base resin and bisphenol-A are obtained fused materials by the present invention under conditions of starvation through mixed melting.
In the present invention, the starvation be in order to prevent air in dioxygen oxidation bisphenol-A, cause synthesize after color of resin become
It is yellow；Present invention preferably employs the mode starvation of nitrogen envelope.
The present invention does not have special restriction to the species of the base resin, using synthesis well known to those skilled in the art
Liquid resin used during epoxy resin.In an embodiment of the present invention, the liquid resin can be specially E51.At this
In invention, the base resin is preferably (please supplement) with the mass ratio of bisphenol-A
The present invention is by the base resin and bisphenol-A mixed melting.In the present invention, the melt temperature is preferably 110
DEG C～130 DEG C, more preferably 115 DEG C～125 DEG C.In the present invention, the heating rate for being warming up to the melt temperature is 1～5
DEG C/min, preferably 1 DEG C/min.The present invention does not have special restriction to the equipment that the mixed melting is adopted, using this area
Reactor known to technical staff；In an embodiment of the present invention, it is preferred to use agitating mode mixing, melting.The present invention
Specification to reactor, agitating mode and heating mode do not have particular/special requirement, according to the technological means known to those skilled in the art
It is stirred in reactor and heats up.
After obtaining fused materials, the present invention mixes the fused materials with catalyst and additive, is warming up to reaction eventually
Temperature is reacted, and obtains modified solid epoxy resin.In the present invention, the additive is the compound containing phenolic hydroxyl group, excellent
Choosing includes one or more in phenol and phenol derivatives, more preferably including p-t-butyl phenol, phenol and p-methyl phenol
In one or more.
In the present invention, the addition of the additive accounts for the ratio of base resin, bisphenol-A, additive and catalyst gross mass
Example is preferably no greater than 5%, more preferably 1～4.5%；In embodiments herein, the ratio of the addition of the additive
0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0% can be specially.
In the present invention, the catalyst preferably includes one or more in triphenylphosphine and triphenylphosphine derivates, more
Preferably include triphenylphosphine, ethyltriphenyl phosphonium chloride phosphine, ethyltriphenylphosphonium bromide, ethyltriphenylphosphiodide iodide phosphine, ethyl triphen
Base acetic acid phosphine and tetraphenylphosphonibromide bromide one or more.
In the present invention, the addition of the catalyst accounts for the ratio of base resin, bisphenol-A, additive and catalyst gross mass
Example is preferably 2 ‰～5 ‰, more preferably 3 ‰～4 ‰.
The present invention mixes fused materials with catalyst and additive, and after obtaining mixture, being warming up to reaction final temperature is carried out
Reaction.
The present invention is more equal in order to base resin, bisphenol-A, additive and catalyst are distributed in building-up process middle-molecular-weihydroxyethyl
Even, the side chain reduced in resin is produced, and using the programming rate less than 5 DEG C/min reaction final temperature is warming up to, and programming rate is more excellent
Elect 1 DEG C/min as.
In the present invention, it is described reaction final temperature be 160 DEG C～180 DEG C, preferably 165 DEG C～175 DEG C, in the enforcement of the application
In example, the reaction temperature can be specially 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C or 180 DEG C；Reaction is in reaction final temperature upper and lower 5
Carry out in DEG C domain of walker；The time of reaction is 60min～120min, preferably 80min～100min, in the enforcement of the application
In example, the reaction time can be specially 60min, 70min, 80min, 90min, 100min, 110min or 120min.
In the present invention, after completing the reaction, preferably the product for obtaining is cooled down, obtain modified solid asphalt mixtures modified by epoxy resin
Fat.In the present invention, there is no particular/special requirement to cooling means, carry out according to technological means well-known to those skilled in the art cold
But, chilling temperature is to room temperature.
The invention provides a kind of method of modifying for reducing solid epoxy viscosity under the conditions of corresponding epoxide equivalent.This
The bright content that by the addition of the compound containing phenolic hydroxyl group, can increase the non-epoxide group in epoxy resin end, can't shadow
The reactivity of hydroxyl on epoxy molecule chain is rung, impact is had no on the bridging property after application solidification.In certain epoxide equivalent
Under the conditions of, being reduced by adding the kinematic viscosity lower limit of additive, epoxy resin, range of viscosities extension breaks through solid ring oxygen tree
The lower viscosity limit of the conventional production of fat.Simultaneously with the reduction of epoxide number, kinematic viscosity changes more with the addition of additive
Substantially.
In order to obtain the weight of each component under the conditions of different epoxide equivalents in the embodiment of the present invention and comparative example, according to
Formulas I and Formula II are calculated：
A={ (aX-bY-cZ)/(X+Y+Z) }-d Formulas I
B=X+Y+Z Formula II
In Formulas I and Formula II, X：The weight of base resin；Y：The weight of bisphenol-A；Z：The weight of p-t-butyl phenol is (when for 0
When without p-t-butyl phenol, synthesized hard resin is that the conventional viscosity under the equivalent is in the viscosity of the method
Limit, can be adjusted according to desired viscosity)；A：Hard resin target epoxide number；B：Total amount of feeding；a：Base resin epoxide number；b：It is double
Phenol A can react hydroxyl value；c：P-t-butyl phenol can react hydroxyl value；d：Experience factor, is by production technology and equipments
The many-sided decision of condition.The value of experience factor is proportional with the size of reactor, heating rate, reaction final temperature, and one
As value be 30～80.
Specifically, in an embodiment of the present invention, the acquisition methods of d are：
First in the ideally calculating each component weight of d=0, under the conditions of nitrogen envelope, by E51 and bisphenol-A in reaction
Mixed using agitating mode in kettle, be warming up to 120 DEG C of melt temperature, E51 and bisphenol-A is melted completely, obtain fused materials；Will
Resulting fused materials mix with additive p-t-butyl phenol and catalyst ethyltriphenylphosphiodide iodide phosphine, with 1 DEG C/min's
Speed is warming up to 175 DEG C of final temperature of reaction and is reacted, and at 175 ± 5 DEG C, cooling after reaction 90min obtains modified solid control temperature
Body epoxy resin, and carry out the repeated experiment no less than 20 times.Survey according to technological means well-known to those skilled in the art
The mean value of the actual epoxide number of examination gained modified epoxy, actual epoxide number and target epoxide number difference, the as synthesis
Under the conditions of experience factor, the present invention in embodiment carry out under identical laboratory condition, reactor volume 1L, heat up speed
1 DEG C/min of rate, reacts 175 DEG C of final temperature, draws d values as 60 with this.
The method that the present invention is provided can also be used to prepare the solid epoxy of setting epoxide equivalent and kinematic viscosity, can
Under the conditions of epoxide equivalent according to a certain restriction, embodiment gained epoxy resin kinematic viscosity value sets median as setting motion
Viscosity number.The addition of thrown additive is set in both additions of embodiment p-t-butyl phenol addition intermediate value, according to
Test result further optimizes the addition of additive, you can obtain meeting the epoxide number of setting, the solid of kinematic viscosity index
Epoxy resin.
In order to further illustrate the present invention, the modified side of the present invention is provided solid epoxy with reference to embodiment
Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
In embodiments of the invention and comparative example, additive adopts p-t-butyl phenol (Aladdin, p-t-butyl phenol
(Korea's brocade lake chemical industry, bisphenol-A contains from E51 (Yang Nong YN1828,185.4g/eq), bisphenol-A for content >=99%), base resin
Amount >=99.91%), catalyst from ethyltriphenylphosphiodide iodide phosphine (the resistance to lucky chemistry of peace, ethyltriphenylphosphiodide iodide phosphine content >=
98.0%)
Embodiment 1：
Sets target epoxide number for 2110mmol/kg epoxy resin, p-t-butyl phenol addition accounts for base resin, double
The 1.5% of phenol A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide
The addition quality of phosphine is 1.1553kg, 0.3222kg, 0.225kg and 450kg.
Under the conditions of nitrogen envelope, E51 and bisphenol-A are mixed in a kettle. using agitating mode, be warming up to melt temperature 120
DEG C, E51 and bisphenol-A is melted completely, obtain fused materials；
Resulting fused materials are mixed with additive p-t-butyl phenol and catalyst ethyltriphenylphosphiodide iodide phosphine, with
The speed of 1 DEG C/min is warming up to 175 DEG C of final temperature of reaction and is reacted, and control temperature is cooled down at 175 ± 5 DEG C after reaction 90min
To modified solid epoxy resin.
Embodiment 2：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, p-t-butyl phenol in the present embodiment
Addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol
It is 1.1520kg, 0.3030kg, 0.045kg and 450kg with the addition quality of ethyltriphenylphosphiodide iodide phosphine.
Embodiment 3：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 1510mmol/kg, calculates adding for E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Enter quality for 1.0918kg, 0.3857kg, 0.0225kg and 450kg.
Embodiment 4：
Modified solid epoxy resin is obtained using the method for embodiment 3, except for the difference that, p-t-butyl phenol in the present embodiment
Addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol
It is 1.0884kg, 0.3666kg, 0.045kg and 450kg with the addition quality of ethyltriphenylphosphiodide iodide phosphine.
Embodiment 5：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 1510mmol/kg, calculates adding for E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Enter quality for 1.0738kg, 0.4037kg, 0.0225kg and 450kg.
Embodiment 6：
Modified solid epoxy resin is obtained using the method for embodiment 5, except for the difference that, p-t-butyl phenol in the present embodiment
Addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol
It is 1.0704kg, 0.3846kg, 0.045kg and 450kg with the addition quality of ethyltriphenylphosphiodide iodide phosphine.
Embodiment 7：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 1100mmol/kg, calculates adding for E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Enter quality for 1.0484kg, 0.4291kg, 0.0225kg and 450kg.
Embodiment 8：
Modified solid epoxy resin is obtained using the method for embodiment 7, except for the difference that, p-t-butyl phenol in the present embodiment
Addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol
It is 1.0450kg, 0.4100kg, 0.045kg and 450kg with the addition quality of ethyltriphenylphosphiodide iodide phosphine.
Embodiment 9：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 770mmol/kg, calculates the addition of E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Quality is 1.0134kg, 0.4641kg, 0.0225kg and 450kg.
Embodiment 10：
Modified solid epoxy resin is obtained using the method for embodiment 9, except for the difference that, p-t-butyl phenol in the present embodiment
Addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, p-t-butyl phenol
It is 1.0101kg, 0.4449kg, 0.045kg and 450kg with the addition quality of ethyltriphenylphosphiodide iodide phosphine.
Embodiment 11：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 710mmol/kg, calculates the addition of E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Quality is 1.0071kg, 0.4704kg, 0.0225kg and 450kg.
Embodiment 12：
Modified solid epoxy resin is obtained using the method for embodiment 11, except for the difference that, to tert-butyl benzene in the present embodiment
Phenol addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, to tert-butyl benzene
The addition quality of phenol and ethyltriphenylphosphiodide iodide phosphine is 1.0037kg, 0.4513kg, 0.045kg and 450kg.
Embodiment 13：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 630mmol/kg, calculates the addition of E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Quality is 0.9986kg, 0.4789kg, 0.0225kg and 450kg.
Embodiment 14：
Modified solid epoxy resin is obtained using the method for embodiment 13, except for the difference that, to tert-butyl benzene in the present embodiment
Phenol addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, to tert-butyl benzene
The addition quality of phenol and ethyltriphenylphosphiodide iodide phosphine is 0.9986kg, 0.4789kg, 0.045kg and 450kg.
Embodiment 15：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 540mmol/kg, calculates the addition of E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Quality is 0.9891kg, 0.4884kg, 0.0225kg and 450kg.Resulting modified solid epoxy resin is designated as H1.
Embodiment 16：
Modified solid epoxy resin is obtained using the method for embodiment 15, except for the difference that, to tert-butyl benzene in the present embodiment
Phenol addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, to tert-butyl benzene
The addition quality of phenol and ethyltriphenylphosphiodide iodide phosphine is 0.9857kg, 0.4693kg, 0.045kg and 450kg.
Embodiment 17：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, sets target epoxy in the present embodiment
It is worth the epoxy resin for 350mmol/kg, calculates the addition of E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine
Quality is 0.9689kg, 0.5086kg, 0.0225kg and 450kg.
Embodiment 18：
Modified solid epoxy resin is obtained using the method for embodiment 17, except for the difference that, to tert-butyl benzene in the present embodiment
Phenol addition accounts for the 3% of base resin, bisphenol-A, additive and catalyst gross mass, calculates E51, bisphenol-A, to tert-butyl benzene
The addition quality of phenol and ethyltriphenylphosphiodide iodide phosphine is 0.9656kg, 0.4894kg, 0.045kg and 450kg.
Comparative example 1：
Modified solid epoxy resin is obtained using the method for embodiment 1, except for the difference that, without to tertiary fourth in this comparative example
Base phenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.1586kg,
0.3414kg, 0kg and 450kg.
Comparative example 2：
Modified solid epoxy resin is obtained using the method for embodiment 3, except for the difference that, without to tertiary fourth in this comparative example
Base phenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0951kg,
0.4049kg, 0kg and 450kg.
Comparative example 3：
Modified solid epoxy resin is obtained using the method for embodiment 5, except for the difference that, without to tertiary fourth in this comparative example
Base phenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0771kg,
0.4229kg, 0kg and 450kg.
Comparative example 4：
Modified solid epoxy resin is obtained using the method for embodiment 7, except for the difference that, without to tertiary fourth in this comparative example
Base phenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0517kg,
0.4483kg, 0kg and 450kg.
Comparative example 5：
Modified solid epoxy resin is obtained using the method for embodiment 9, except for the difference that, without to tertiary fourth in this comparative example
Base phenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0168kg,
0.4832kg, 0kg and 450kg.
Comparative example 6：
Modified solid epoxy resin is obtained using the method for embodiment 11, except for the difference that, without to uncle in this comparative example
Butylphenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0104kg,
0.4896kg, 0kg and 450kg.
Comparative example 7：
Modified solid epoxy resin is obtained using the method for embodiment 13, except for the difference that, without to uncle in this comparative example
Butylphenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 1.0019kg,
0.4981kg, 0kg and 450kg.
Comparative example 8：
Modified solid epoxy resin is obtained using the method for embodiment 15, except for the difference that, without to uncle in this comparative example
Butylphenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 0.9924kg,
0.5076kg, 0kg and 450kg.
Comparative example 9：
Modified solid epoxy resin is obtained using the method for embodiment 17, except for the difference that, without to uncle in this comparative example
Butylphenol, calculate E51, bisphenol-A, p-t-butyl phenol and ethyltriphenylphosphiodide iodide phosphine addition quality be 0.9723kg,
0.5277kg, 0kg and 450kg.
Solid epoxy viscosity determining procedure reference standard：ASTMD445-2012 is transparent and opaque liquid kinetic viscosity
The calculating of test method and dynamic viscosity.Analysis result is as shown in table 1：
The solid epoxy viscosity test results that the embodiment of the present invention of table 1 and comparative example are obtained
According to the data of table 1, as the addition of p-t-butyl phenol rises, the viscosity of solid epoxy substantially drops
Low, such as the testing result of comparing embodiment 1, embodiment 2 and comparative example 1, by adding, p-t-butyl phenol is modified to glue motion
Degree drops to 6.3m2/ below s, breaks through the lower viscosity limit of the conventional production of No. 1 hard resin.Simultaneously with the reduction of epoxide number, fortune
Kinetic viscosity is more obvious with the addition change of p-t-butyl phenol.
And the solids epoxy of the kinematic viscosity needed for the addition of p-t-butyl phenol is obtained can be adjusted according to result
Resin.According to embodiment 15, the experimental result of embodiment 16, synthesizing epoxy value can be attempted and glued for 540 ± 5mmol/kg, motion
Spend the 8.5 ± 0.1m of epoxy resin for both medians2/ s, the addition that will throw p-t-butyl phenol is set in both additions
Amount intermediate value 2.4%, and according to gained test result, further (viscosity is bigger than normal, increases for the addition of adjustment p-t-butyl phenol
0.1% PTBP amounts；Viscosity is less than normal, reduces 0.1%PTBP amounts, optimizes the addition of PTBP), can obtain meeting epoxide number and be
540 ± 5mmol/kg, kinematic viscosity are 8.5 ± 0.1m2The resin of/s indexs.
The method of modifying of the solid epoxy of present invention offer is provided by above example and comparative example, can
Reduce viscosity under the conditions of corresponding epoxide equivalent.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of method of modifying of solid epoxy, comprises the following steps：
(1) under the conditions of starvation, by base resin and bisphenol-A mixed melting, fused materials are obtained；
(2) fused materials that the step (1) is obtained are mixed with additive and catalyst, is warming up to reaction final temperature and is incubated
Reaction, obtains modified solid epoxy resin, and the additive is the compound containing phenolic hydroxyl group；
The addition of the additive accounts for the ratio of base resin, bisphenol-A, additive and catalyst gross mass and is not more than 5%；
The catalyst includes one or more in triphenylphosphine and triphenylphosphine derivates；
Reaction final temperature in the step (2) is 160 DEG C～180 DEG C；
The temperature retention time of reaction is 60min～120min in the step (2).
2. method of modifying according to claim 1, it is characterised in that the additive is included in phenol and phenol derivatives
One or more.
3. the method for modifying according to any one of claim 1 and 2, it is characterised in that the additive is included to tertiary fourth
One or more in base phenol, phenol and p-methyl phenol.
4. method of modifying according to claim 1, it is characterised in that the catalyst includes triphenylphosphine, ethyl triphen
Base phosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphiodide iodide phosphine, ethyl triphenyl acetic acid phosphine and tetraphenylphosphonibromide bromide are a kind of
Or it is several.
5. method of modifying according to claim 1, it is characterised in that the catalyst charge account for liquid epoxies,
2 ‰～the 5 ‰ of bisphenol-A, additive and catalyst gross mass.
6. method of modifying according to claim 1, it is characterised in that the speed heated up in the step (2) is 1～5 DEG C/
min。
7. method of modifying according to claim 1, it is characterised in that the speed of the intensification of the step (2) is 1 DEG C/
min。
8. method of modifying according to claim 1, it is characterised in that in the step (1) temperature of melting be 110 DEG C～
130℃。
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| CN110591055B (en) * | 2019-08-20 | 2022-08-30 | 浙江万盛股份有限公司 | Cardol epoxy resin and preparation method thereof |
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