CN1103650A

CN1103650A - Epoxy resin firming agent with poly-functional group in molecula and its processing method

Info

Publication number: CN1103650A
Application number: CN 93115956
Authority: CN
Inventors: 朴万成
Original assignee: Individual
Current assignee: Individual
Priority date: 1993-12-11
Filing date: 1993-12-11
Publication date: 1995-06-14

Abstract

The said epoxy resin curing agent consists of primary and secondary amines in 50-60%, binary alcohols in 20-30% and binary acids in 20-30%. It is prepared in reactor in the heating and negative-pressure conditions by adding first the binary alcohols and binary acids and then the amines compound or mixture.

Description

Epoxy resin firming agent with poly-functional group in molecula and its processing method

The invention belongs to a kind of epoxy curing agent.

At present, Resins, epoxy is with a wide range of applications in various industrial circles, reason is that Resins, epoxy is that the tackiness agent that base-material prepares has unique adhesion property, be that other adhesive agent is incomparable, have higher physical strength, less shrinkability, resistant to chemical media, being a kind of structure glue of every high comprehensive performance, is the indispensable industrial chemicals of every field such as national defense industry, industrial or agricultural, light industry, must mix good solidifying agent in use.The kind of epoxy curing agent is more now, amine is arranged, anhydrides, the Versamid class, can be divided into low temperature by temperature, empty temperature, in gentle high temperature type, life-time service the quadrol solidifying agent arranged, its shortcoming is volatile, pungency is big, the toxicity height, big, wayward with Resins, epoxy mixing thermal discharge, consumption is strict, curing performance is bad, as other aliphatic inclined to one side amine, secondary amine and modified amine, though reduced pungency, curing performance is still not ideal enough, anhydrides solidified Resins, epoxy, resistance toheat is than higher, and electrical property is better, but its weak point is that media-resistant and humidity resistance are relatively poor, normal temperature great majority down is solid, difficulty is mixed with Resins, epoxy, though the liquid acid anhydrides of modification is arranged, all needs to be heating and curing, use inconvenience, Versamid promptly is that solidifying agent is again a toughner, and amount ranges is wide, and working life is long, easy to operate, volatility is little, and toxicity is very low, can empty temperature cured epoxy resin, low temperature is difficulty, because the raw material that Versamid adopts is linolic acid two polyesters, raw material sources are limited, and extensively large-area applications is restricted.

For solving the deficiency of above several solidifying agent, the invention provides a kind of multi-functional epoxy curing agent that has, be specially the epoxy curing agent that contains amido, carboxyl and amide group, make it have the amine curing agent ambient cure, usage quantity is little; The acid anhydride type curing agent thermotolerance is strong, good electrical property; The epoxy curing agent of advantages such as the Versamid bonding force is strong, and increasing tougheness is good.

Raw materials used and the percentage composition of epoxy curing agent of the present invention.

1. aliphatics and aromatic primary amine, secondary amine, be 50～50%(wt), raw materials used primary amine, secondary amine are pure combinations, also can adopt blending ingredients, and wherein pure component has quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine; Blending ingredients can be the mixing of any two kinds of formula various kinds of amine in the pure component, also can be the heavy constituent of association when producing pure component.

2. aliphatic di-alcohols is 20～30%, comprises the dibasic alcohol that contains 2～10 carbon in the molecule, and wherein commonly used have ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, hexylene glycol, a decanediol.

3. aliphatics, aromatic diprotic acid or acid anhydrides are 20～30%, and comprising saturated, the unsaturated dibasic acid class that contain 2～18 carbon in the molecule, wherein the present invention adopts oxalic acid, hexanodioic acid, phthalic acid.

The solidifying agent preparation method:

According to the above ratio, dibasic alcohol with 20～30%(wt) and 20～30% diprotic acid add in the reactor, under negative pressure 50～80 mmhg, temperature is 100 ℃～200 ℃ and reacted 6 hours down, again 50～60% aminated compounds or mixture are added in the reactor, under negative pressure 50～80 mmhg, temperature 60 ℃～200 ℃ down 4 hours resultants of reaction be the present invention's solidifying agent, wherein order of addition(of ingredients) adds change less, and the solidification effect that then generates solidifying agent also changes to some extent.

The present invention is at amine for synthesized solidified dose, anhydrides, what synthesize on the basis of Versamid class solidifying agent has an amine curing agent ambient cure, the acid anhydride type curing agent thermotolerance is strong, good electrical property, Versamid class solidifying agent is toughness reinforcing, the novel solidifying agent of advantages such as bonding force is strong, because solidifying agent of the present invention has adopted mixed amine and heavy constituent amine on synthetic, dibasic alcohol and diprotic acid, make the solidifying agent molecule possess many groups, accelerated curing speed on the one hand, also improved simultaneously the overall target of epoxy resin glue, because the present invention is flexible and changeable on raw material uses, thereby the synthesizing amide key solidifying agent that is through with must adopt the synthetic method of pure component amine and linolic acid two polyesters, so the present invention's advantage is: raw material uses flexibly, and is synthetic convenient, high comprehensive performance, product price is cheap, can promote the use of.

The present invention's embodiment:

The phthalic anhydride that in reactor, adds 25 parts of heavy ethylene glycol and 25 parts of weights, under negative pressure 50 mmhg, heat 120 ℃ and reacted 6 hours down, reduce to 60 ℃ of hexanediamines that slowly add 50 parts, under negative pressure 50 mmhg, heat 80 ℃ and react the liquid of producing in 4 hours, be epoxy curing agent.By the product of above embodiment production, shearing resistance, tensile strength be all greater than amine, smaller or equal to the amides solidifying agent, and 12 hours cured epoxy resins of normal temperature, hardener dose can account for Resins, epoxy about 30%.

Claims

1, contain multi-functional epoxy curing agent in a kind of molecule, it is characterized in that this solidifying agent is by following elementary composition and weight percentage:

1) aliphatics and aromatic primary amine, secondary amine 50～60% (wt);

2) aliphatic di-alcohols 20%～30%; Comprise the dibasic alcohol that contains 2～10 carbon in the molecule, wherein commonly used have ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, hexylene glycol, a decanediol.

3) aliphatics, aromatic diprotic acid or acid anhydrides 20～30%;

Wherein raw materials used primary amine, secondary amine are pure combinations, also can adopt blending ingredients, and pure component has quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine; Blending ingredients can be the mixing of any two kinds of formula various kinds of amine in the pure component, also can be the heavy constituent of association when producing pure component; Wherein aliphatic di-alcohols is the dibasic alcohol that contains 2～10 carbon in the molecule, and wherein commonly used have ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, hexylene glycol, a decanediol; Wherein aliphatics, aromatic diprotic acid are to comprise saturated, the unsaturated dibasic acid class that contains 2～18 carbon in the molecule, and the present invention adopts oxalic acid, hexanodioic acid, phthalic acid.

2, the preparation method who contains multi-functional epoxy curing agent in a kind of molecule, it is characterized in that dibasic alcohol and 20%～30% diprotic acid with 50%～60%(wt) add in the reactor, under negative pressure 50～80 mmhg, temperature is 100 ℃～200 ℃ and reacted 6 hours down, again with in 20%～30% the aminated compounds or mixture adding reactor, under negative pressure 50～80 mmhg, temperature was reacted 4 hours down at 60 ℃～200 ℃, and resultant promptly is an epoxy curing agent.