CN1053683C - Multifunctional resin curing agent II and preparation thereof - Google Patents
Multifunctional resin curing agent II and preparation thereof Download PDFInfo
- Publication number
- CN1053683C CN1053683C CN96117010A CN96117010A CN1053683C CN 1053683 C CN1053683 C CN 1053683C CN 96117010 A CN96117010 A CN 96117010A CN 96117010 A CN96117010 A CN 96117010A CN 1053683 C CN1053683 C CN 1053683C
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- resin
- curing
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- resol
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Abstract
The present invention belongs to the technical field of resin curing and provides a universal multifunction resin curing agent II which can be applied to the curing under the heating condition of epoxy resin and the curing of a mixture of phenolic resin and furan resin. A curing active species of the curing agent has two or more kinds of curing functional groups with different properties (not only-NH2 and/or-CONH2 functional groups, but also-SO3 H functional groups) and stage A phenolic resin or furan resin. The present invention with a wide application range and high universality has the characteristics of high activity, fire resistance, low toxicity, stabilization, no volatilization, corrosion or pollution, etc.
Description
The invention belongs to the organic chemistry class, relate to the resin solidification technical field.
Solidifying agent is a kind of can the generation or initiating chamical reaction with resin (natural or synthetic), makes resin by the liquid solid state that is converted into, and makes it to have the compound of certain mechanical strength and cohesive force and corrosion resistant performance.If various resins lack the effect of solidifying agent, just lost its use value.This shows that solidifying agent is how important to the curing of resin.Solidifying agent in use deal only accounts for a seldom part, generally only accounts for the 5-20% of weight resin.Solidifying agent is divided into mineral-type solidifying agent and organic class solidifying agent two big classes.
At present, synthetic resins commonly used both at home and abroad has except that unsaturated polyester resin: three major types such as Resins, epoxy, resol, furans (chaff ketone) resin.
Curing agent for epoxy resin has derivatives class solidifying agent, half latent curing agent, acid anhydride type curing agent and the resene solidifying agent etc. of aromatic amine solidifying agent, aliphatics amine solidifying agent, tertiary amines solidifying agent, secondary amine class solidifying agent, amine.
Phenolic resin curative has benzene sulfonyl chloride, p-methyl benzene sulfonic chloride, sulfovinic acid, mahogany acid, dodecyl sodium sulfonate and naphthene sulfonic acid etc.
Furan resin hardener has sulfovinic acid, benzene sulfonyl chloride, p-methyl benzene sulfonic chloride, phosphoric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid etc.
Only contain a kind of functional group of the same type in the molecular structure of above-mentioned all class solidifying agent, as amine (NH
2) basic, acid amides (CONH
2) basic, sulfonic acid (SO
3H) base or SULPHURYL CHLORIDE (SO
2Cl) base etc., and these single functional groups only can have an effect and demonstrate its distinctive sense at a kind of (class) resin, and just can not have an effect to inhomogeneous resin.In other words, has amine (NH
2) base and or acid amides (CONH
2) solidifying agent of base class functional group, can only play solidification to Resins, epoxy, and have sulfonic acid (SO
3H) base and or SULPHURYL CHLORIDE (SO
2Cl) solidifying agent of base class functional group can only play solidification to resol and furane resin.
96116848.X application for a patent for invention is exactly to exist at above-mentioned all solidifying agent to have only unitary class functional group and can only a kind of resin be played the defective of solidification and propose to have in a kind of solidifying agent the above inhomogeneity of two or two functional group, makes it to have the multifunctional resin curing agent that can both have an effect with Resins, epoxy, resol, furane resin or their mixture.
The objective of the invention is on the basis of 96116848.X application for a patent for invention, increase A stage resol or furane resin component, make further raising curing activity, reduce cost, save material, propose a kind of Multifunction resin curing agent (II).
Principle of the present invention is based on the amine (NH that can play solidification with Resins, epoxy in the curing activity body molecular structure that makes in a kind of multifunctional resin curing agent
2) basic functional group and or acid amides (CONH
2) basic functional group, the sulfonic acid (SO that can play solidification with resol or furane resin is arranged again
3H) basic functional group also has A stage resol or furane resin composition.Curing activity body in this class multifunctional resin curing agent (II) has the organic compound of structure shown in the following general formula (I):
R (SO
3H) n
1Mn
2R
2n(I) R is aryl derivatives parents such as phenol, dihydroxyphenyl propane, naphthols in the formula (I);
M is [CO (NH
2)
2] n
3[R
1(NH
2)
2] n
4
R
1Be alkyl, aryl etc.;
R
2Be A stage resol or furane resin;
N is 1,2
n
1Be 1~4;
n
2Be 1~4;
n
3Be 0,1,2
n
4Be 1,2
This compounds or single or mixing cooperate with solvent, toughner just becomes multifunctional resin curing agent of the present invention (II).
Technical scheme of the present invention is preparation above-mentioned general formula (I) R (SO
3H) n
1Mn
2R
2nOrganic compound and mixture, promptly follow these steps to condition synthetic successively at the three-necked bottle that has 1500ml whipping appts and that place water-bath.
1, in three-necked bottle, injects the vitriol oil (or oleum or SO
3) 4~4.1mol, be preheated to 60~100 ℃, constantly stirring under (controlling 80~120 rev/mins) situation, add the 1mol parent lentamente then, carry out sulfonation as dihydroxyphenyl propane, in half an hour, add, reacted about 1 hour.See reaction formula (2)
2, hot elimination removes the intact resistates of unreacted, with standby.
3, the urea that adds 4~4.5mol again in filtrate under stirring condition, reacts half an hour under less than 80 ℃ of temperature.See reaction formula (3)
4, under stirring and cooling situation, in three-necked bottle, add the quadrol of 4~12mol more lentamente, temperature is controlled at about 0~15 ℃, reacts in about 3 hours.See reaction formula (4)
5, under stirring condition, holding temperature 50-60 ℃, in three-necked bottle, add A stage resol or furane resin 1-4mol again, react and finished in 2 hours, see reaction formula (5).
6, the curing activity body R (SO that above-mentioned reaction is generated
3H) n
1Mn
2R
2nBe re-dubbed multifunctional resin curing agent (II) with quantitative polar solvent, toughner.Its prescription is as follows: curing activity body [R (SO
3H) n
1Mn
2R
2n] 170~200 parts of 20 parts of compound methods of 100 parts of toughner of polar solvent (as ethanol or water etc.) (as butyl ester or monooctyl ester etc.): under continuous stirring state, with R (SO
3H) n
1Mn
2R
2nAdd lentamente in the polar solvent, treat that it all after the dissolving, adds toughner again, stirring gets final product.The reaction equation of above steps is as follows:
(3)
(4)
(5)
Annotate: R represents dihydroxyphenyl propane, R in above-mentioned reaction formula (2), (3), (4), (5)
3Represent the chain link of A stage resol; N is 1,2 n
5Be 1~4.
Key problem in technology of the present invention is that the multifunctional resin curing agent formula of is R (SO
3H) n
1Mn
2R
2nThe curing activity body in must contain plural functional group of different nature, can work with epoxy and epoxy thereof and phenolic aldehyde, furans hybrid resin, in conjunction with being stable, and Decomposition no longer takes place, and has multidirectional selectivity function, can cooperate with multiple solvent or auxiliary agent, and this organic compound has anti-flaming function.
Characteristics of the present invention are to have two or more functional groups of different nature owing in this curing activity body organic compound molecule structure, therefore, and can be at room temperature or the lower following cured epoxy resin of temperature (10 ℃); Also can be under heating condition (60~90 ℃) phenolic resin cured or furane resin; Can cured epoxy resin be main ingredient under low temperature or room temperature also, resol or furane resin be the hybrid resin of auxiliary component; Also can solidify with resol or furane resin under heating condition be main ingredient, and Resins, epoxy is the hybrid resin of auxiliary component.Because this solidifying agent itself has anti-flaming function, so can reduce the combustibility of resin.This solidifying agent can also be under wet condition or in the water cured resin, this solidifying agent also has low toxicity, water-soluble, shelf-stable, non-volatile, no burn into is free from environmental pollution.Owing in this curing activity body organic compound molecule structure A stage resol or furane resin are arranged, so solidifying agent of the present invention further improves curing activity.Again owing to increased A stage resol or furane resin composition in the curing activity body, and in multifunctional resin curing agent (II) curing activity body constant rate, thereby saved the expensive component of other valency in the curing activity body, as quadrol etc.Therefore, can reduce cost, save material behind the use multifunctional resin curing agent (II).Applied widely, the highly versatile of this solidifying agent.
Embodiment:
(1) epoxy resin cure
Resins, epoxy (E
44) 100 parts
15~20 parts of multifunctional resin curing agents (II)
The some conditions of cure of Graphite Powder 99: room temperature or 10 ℃, relative humidity) 85%, 6~8 hours set times.
(2) resol is main component, and Resins, epoxy is the curing of auxilliary component:
70 parts in resol (or furane resin)
Resins, epoxy (E
44) 30 parts
15~20 parts of multifunctional resin curing agents (II)
The some conditions of cure of Graphite Powder 99: under 60~90 ℃, 6~8 hours set times.
(3) Resins, epoxy is major constituent, and resol (furane resin) is that auxilliary component is solidified:
Resins, epoxy (E
44) 70 parts
30 parts in resol (or furane resin)
15~20 parts of multifunctional resin curing agents (II)
The some conditions of cure of Graphite Powder 99: room temperature or 10 ℃, relative humidity>85%, 6~8 hours set times
(4) solidify in the Resins, epoxy water
Resins, epoxy (E
44) 100 parts
15~20 parts of multifunctional resin curing agents (II)
The some conditions of cure of Graphite Powder 99: room temperature, in the water, 6~8 hours set times
The present invention can use following scope:
1, the curing of epoxy resin adhesive liquid, clay, binding agent.
2, take epoxy resin as Main Components, phenolic resins or furane resins are the curing of the glue of minor consistuent, clay, binding agent.
3, take phenolic resins or furane resins as Main Components, epoxy resin is glue, the clay of minor consistuent, the curing of binding agent.
4 and be the curing of the various reinforced plastics of binding agent according to this three resinoid and mixture.
Claims (3)
1. resin curing agent, it is made up of curing activity body, polar solvent, toughner, it is characterized in that the proportioning of this solidifying agent is as follows:
Curing activity body 170-200 part (weight)
100 parts of polar solvents (weight)
20 parts of toughner (weight)
Wherein the curing activity body is by containing resol, furan resin hardener feature
Sulfonic group and contain the epoxy curing agent feature amido, amide group and
The structural formula that contains A stage resol, furane resin formation is the organic of I
The mixture of compound:
Structural formula I R (SO
3H)
N1M
N2R
2n
Among the formula I: R is the aryl derivatives parent;
M is [CO (NH
2)
2]
N3[R
1(NH
2)
2]
N4
N is 1,2
n
1Integer for 1-4;
n
2Integer for 1-4;
n
3Be 0,1,2;
n
4Be 1,2;
R
1Be alkyl or aryl; R
2Be A stage resol, furane resin
Its curing activity body is made by following steps successively:
A) the 4-4.1mol vitriol oil under 60-100 ℃ of temperature or oleum or SO
3In under whipped state, slowly add 1mol aryl derivatives parent R and carried out sulfonation 1 hour;
B) after the heat filter, under stirring condition, in filtrate, add 4-4.5mol urea CO (NH
2)
2, reacting half an hour down less than 80 ℃;
C) under stirring and cooling situation, slowly add the 4-12mol quadrol, controlled temperature 0-15 ℃, reacted 3 hours.
D) under whipped state, holding temperature 50-60 ℃, add A stage resol.
2. the preparation method of a resin curing agent, the compound method that it is characterized in that it is as follows: under continuous stirring state, add the curing activity body in the polar solvent lentamente, after treating its whole dissolvings, add toughner again, stirring gets final product, and wherein the curing activity body is made by following steps successively:
A) the 4-4.1mol vitriol oil under 60-100 ℃ of temperature or oleum or SO
3In under whipped state, slowly add 1mol aryl derivatives parent R and carried out sulfonation 1 hour;
B) after the heat filter, under stirring condition, in filtrate, add 4-4.5mol urea CO (NH
2)
2, reacting half an hour down less than 80 ℃;
C) under stirring and cooling situation, slowly add the 4-12mol quadrol, controlled temperature 0-15 ℃, reacted 3 hours.
D) under whipped state, holding temperature 50-60 ℃, add A stage resol.
3. the preparation method of resin curing agent according to claim 2 is characterized in that aryl derivatives parent R is phenol or dihydroxyphenyl propane or naphthols, and the four step representative reactions formulas that the curing activity system is equipped with are:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN96117010A CN1053683C (en) | 1996-07-10 | 1996-07-10 | Multifunctional resin curing agent II and preparation thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN96117010A CN1053683C (en) | 1996-07-10 | 1996-07-10 | Multifunctional resin curing agent II and preparation thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1170011A CN1170011A (en) | 1998-01-14 |
CN1053683C true CN1053683C (en) | 2000-06-21 |
Family
ID=5123954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96117010A Expired - Fee Related CN1053683C (en) | 1996-07-10 | 1996-07-10 | Multifunctional resin curing agent II and preparation thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1053683C (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106881445B (en) * | 2017-02-08 | 2019-08-06 | 宁夏共享化工有限公司 | A kind of furan resin casting is with applying curing agent and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5538873A (en) * | 1979-07-27 | 1980-03-18 | Sanyo Chem Ind Ltd | Preparation of amine modified product |
JPS57195119A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
CN85107222A (en) * | 1984-11-16 | 1986-05-10 | 三菱电机股份有限公司 | Epoxy resin composition |
CN85100228A (en) * | 1985-04-01 | 1986-09-24 | 武汉大学 | Photosensitive PN junction side direction is injected the indirect coupling method of electric device |
CN87101669A (en) * | 1987-02-27 | 1988-09-07 | 项新 | Curing agent capable of enhancing toughness of epoxy resin |
JPH0480227A (en) * | 1990-07-20 | 1992-03-13 | Mitsui Toatsu Chem Inc | Curing agent for epoxy resin |
CN1103650A (en) * | 1993-12-11 | 1995-06-14 | 朴万成 | Epoxy resin firming agent with poly-functional group in molecula and its processing method |
-
1996
- 1996-07-10 CN CN96117010A patent/CN1053683C/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5538873A (en) * | 1979-07-27 | 1980-03-18 | Sanyo Chem Ind Ltd | Preparation of amine modified product |
JPS57195119A (en) * | 1981-05-25 | 1982-11-30 | Mitsubishi Gas Chem Co Inc | Preparation of curing agent for epoxy resin |
CN85107222A (en) * | 1984-11-16 | 1986-05-10 | 三菱电机股份有限公司 | Epoxy resin composition |
CN85100228A (en) * | 1985-04-01 | 1986-09-24 | 武汉大学 | Photosensitive PN junction side direction is injected the indirect coupling method of electric device |
CN87101669A (en) * | 1987-02-27 | 1988-09-07 | 项新 | Curing agent capable of enhancing toughness of epoxy resin |
JPH0480227A (en) * | 1990-07-20 | 1992-03-13 | Mitsui Toatsu Chem Inc | Curing agent for epoxy resin |
CN1103650A (en) * | 1993-12-11 | 1995-06-14 | 朴万成 | Epoxy resin firming agent with poly-functional group in molecula and its processing method |
Also Published As
Publication number | Publication date |
---|---|
CN1170011A (en) | 1998-01-14 |
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