Embodiment
Epoxy resin (A)
The epoxy resin (A) that reaches described in the present invention can use well-known liquid state or solid epoxy under the room temperature condition, comprises diphenylol propane epoxy resin, organic-silicon-modified diphenylol propane epoxy resin; Bromine modification diphenylol propane epoxy resin, chlorine modification diphenylol propane epoxy resin, diphenylol propane side chain type epoxy resin, the many epoxy resin of phenolic aldehyde; Glycerol epoxy resin, fatty acid glycerine ester epoxy resin, alicyclic Racemic glycidol fat, epoxy silicone; Four phenolic group epoxy resin, resorcinol type epoxy, tricyanic epoxy resin, bicyclopentadiene dioxide expoxy resin; Vinyl cyclohexene dioxide epoxy resin, polybutadiene epoxy resin, titanium dioxide double cyclopentenyl ether resin, biphenyl type epoxy resin; The phenol aralkyl-type epoxy resin, naphthalene type epoxy resin contains amino-type epoxy resin; The line style aliphatic epoxy resin, cycloaliphatic epoxy resin, a kind of in the Racemic glycidol ether type epoxy or their mixture etc.Wherein be preferably bisphenol A-type and bisphenol f type epoxy resin.
Composite solidifying agent of epoxy resin (B)
(B) composite curing agent that reaches according to the invention is the composite curing agent system that contains aromatic amine curing agent, and aromatic amine curing agent B1 comprises mphenylenediamine in this system, m-xylene diamine, 4,4 '-diaminodiphenyl-methane; 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl oxide; 4,4 '-N, N '-dimethylamino ditane, 6; 6 '-two chloro-4,4 '-diaminodiphenyl-methane, 5,5 '-dimethyl--4; 4 '-diaminodiphenyl-methane, benzene dimethylamine, m-aminophenyl methylamine etc., above-mentioned aromatic amine curing agent can be separately or two kinds and above mixing be used in the composite curing agent system; Epoxy curing agent B2 with the compound use of aromatic amine curing agent in this (B) composite curing agent system comprises Dyhard RU 100 and modification Dyhard RU 100 class solidifying agent; Bismaleimides; PHB etc., perhaps both and above and the compound use of aromatic amine curing agent separately of above-mentioned these three types of epoxy hardeners; Be somebody's turn to do the equivalent of the reactive base of (B) composite curing agent; With respect to the normal more satisfactory of the epoxy group(ing) of (A) epoxy resin is 0.1≤(solidifying agent)/(epoxy resin)≤3.0; Better is 0.8≤(solidifying agent)/(epoxy resin)≤1.25; Equivalence ratio has a part of unreacted not in above-mentioned scope the time, can cause product performance to break down; The equivalence ratio of the reactive base of above-mentioned aromatics solidifying agent B1 and solidifying agent B2 can be 0.01~99 in this (B) composite curing agent system, and comparatively ideal equivalence ratio is 0.25~4, and better equivalence ratio is 0.5~2.
Other compositions
Except that above-mentioned each composition, not damage the object of the invention, according to the needs of the finished product purposes; Can further add additive in compsn of the present invention, additive comprises: epoxy curing agent promotor, epoxide resin reactive diluent; Epoxide resin reactive toughner; Mineral filler, silane coupling agent, tinting material etc.
Above-mentioned epoxy resin cure promotor comprises imidazole curing agent promotor such as imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole; Above-mentioned curing catalyst can use separately or can make up two or more common uses simultaneously; With 100 parts by weight of epoxy resin is benchmark, and the content of this curing catalyst is 0~1.0 weight part.
Above-mentioned epoxide resin reactive diluent comprises single epoxy group(ing) reactive thinner (for example propylene oxide, glycidyl allyl ether etc.), many epoxy group(ing) reactive thinner (diglycidylether for example; The divinyl bis-epoxy; Bicyclopentadiene dioxide etc.), triphenyl phosphite and r-GBL etc., these epoxide resin reactive diluents can use a kind of separately; Two kinds or two or more uses also capable of being combined; Can be according to the needs of product end-use, its usage quantity is with respect to total 100 mass parts of above-mentioned (A)~(B), and addition is 0 mass parts~40 mass parts.
Above-mentioned epoxide resin reactive toughner comprises epoxy compounds class endurable active toughener (for example epoxy glycerite lipid, epoxy fatty acid monoester class etc.), viton class endurable active toughener (thiorubber for example; The paracril class, X 050, urethanes; Chlorosulfonated polyethylene rubber etc.), polyamide resin lipid endurable active toughener (for example low-molecular-weight polyamide resin, modified polyamide resin etc.); Polyester resin endurable active toughener (for example W 166 ethers, polyglycerol ethers etc.), these epoxide resin reactive toughner can use a kind of separately; Two kinds or two or more uses also capable of being combined; Can be according to the needs of product end-use, its usage quantity is with respect to total 100 mass parts of above-mentioned (A)~(B), and addition is 0 mass parts~50 mass parts.
Above-mentioned mineral filler can be used well-known mineral filler, for example: silicon dioxide powder, aluminum oxide; White titanium pigment; Talcum powder etc., these fillers can use a kind of separately or make up two kinds or two or more uses, can be according to the needs of product end-use; Its usage quantity is with respect to total 100 mass parts of above-mentioned (A)~(B), and addition is 0 mass parts~80 mass parts.
Screw extrusion press
The screw extrusion press that reaches according to the invention comprises single screw extrusion machine, intermeshing counter-rotating twin-screw forcing machine or non-intermeshing counter-rotating twin-screw forcing machine; The engagement co-rotating twin screw extruder; The length-to-diameter ratio of screw extrusion press (L/D) is 15/1~100/1; Preferably get 45/1~70/1 this scope; Select engagement co-rotating twin screw extruder best results, the engagement co-rotating twin screw extruder is the effects of hunger device, can be through the control inlet amount; Processing parameters such as screw speed and the setting of extruder barrel temperature are controlled the material reaction residence time and B scalariform attitude epoxy resin level of response, thereby obtain the distincter composition epoxy resin of softening temperature.
Preparation is extruded in the reaction of the composition epoxy resin of B scalariform attitude
The present invention adopts the reaction extrusion molding to prepare B scalariform attitude composition epoxy resin, promptly is reactor drum with the screw extrusion press, with above-mentioned epoxy resin (A); Composite solidifying agent of epoxy resin (B) is sent into screw extrusion press and is reacted, 0~60 ℃ of screw extrusion press feeding section temperature, 60~180 ℃ of melt zone temperature; 100~200 ℃ of mixing conversion zone temperature, 180~200 ℃ of discharging section temperature, screw speed will be controlled at 20~300rpm; When rotating speed is lower than 20rpm; Cause the overstand of material, mix inhomogeneously, production efficiency is low; When rotating speed is higher than 300rpm; Can cause the high molecular polymer shear degradation and the residence time not enough; Therefore, control screw speed and inlet amount are controlled between 30~1200s the mean residence time of material in screw extrusion press; Better is to be controlled between 600~900S, promptly obtains product through overcooling conveying and fragmentation again; Further can optionally send into above-mentioned additive according to the needs of the finished product performance as other compositions, additive can with above-mentioned mixing of materials after directly send into forcing machine from feeding section, also can be in fusion transportation section input forcing machine.
The present invention further optimizes and adopts different reinforced preparation methods according to epoxy resin (A) raw material different state at normal temperatures.
Be all liquid state under the above-mentioned epoxy resin of the present invention (A) normal temperature, when perhaps being liquid at normal temperatures behind the uniform mixing, adopt the preparation method a of the B scalariform attitude composition epoxy resin of optimizing; It is even to comprise the steps: that above-mentioned epoxy resin (A) and composite solidifying agent of epoxy resin (B) are joined in the premixer thorough mixing successively, and in the mixing process, premixer can suitably heat and promote to mix; But temperature of charge should not surpass 60 ℃ in the premixer, more mixed material is sent into to react in the screw extrusion press afterwards and extrudes, in reinforced process; Premixer preferably keeps whipped state; Further, can also can optionally send into above-mentioned additive according to the needs of the finished product performance as other compositions; Additive can directly be sent into forcing machine from feeding section behind the thorough mixing with above-mentioned material in premixed device; Also can be in fusion transportation section input forcing machine, last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation.
Above-mentioned epoxy resin (A) is all when solid-state among the present invention, can adopt the preparation method b1 of optimization, comprises the steps: epoxy resin (A) and composite solidifying agent of epoxy resin (B) through mixing tank with powdery uniform mixing each other; Preferably; Mixing tank has the temperature rise of chuck to avoid causing owing to friction that can lead to water coolant, afterwards, more mixed material is sent into to react in the screw extrusion press and extrudes; Can also be according to the needs of the finished product performance; Can optionally send into above-mentioned additive as other compositions, additive can directly be sent into forcing machine from feeding section behind the thorough mixing with above-mentioned material in premixed device, also can be in fusion transportation section input forcing machine; Last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation.
Above-mentioned epoxy resin (A) is all when solid-state among the present invention; Also can adopt the another kind of preparation method b2 that optimizes; Comprise the steps: earlier composite solidifying agent of epoxy resin (B) and part solid epoxy resin (A) through forcing machine or rotate the solid epoxy resin masterbatch that roller is prepared into the powdered epoxy composite curing agent, afterwards, again with the epoxy resin (A) of rest part and composite solidifying agent of epoxy resin masterbatch through mixing tank with powdery uniform mixing each other; Preferably; Mixing tank has the temperature rise of chuck to avoid causing owing to friction that can lead to water coolant, afterwards, more mixed material is sent into to react in the screw extrusion press and extrudes; Can also be according to the needs of the finished product performance; Can optionally send into above-mentioned additive as other compositions, additive can directly be sent into forcing machine from feeding section behind the thorough mixing with above-mentioned material in premixed device, also can be in fusion transportation section input forcing machine; Last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation.
Above-mentioned epoxy resin (A) component is made up of liquid-state epoxy resin (A1) and solid epoxy resin (A2) among the present invention; Can adopt the preparation method c1 of optimization; Comprise the steps: above-mentioned solid epoxy resin (A2) and composite solidifying agent of epoxy resin (B) through premixer with powdery uniform mixing each other; Preferably; Premixer has the temperature rise of chuck to avoid causing owing to friction that can lead to water coolant, more mixed material is sent in the screw extrusion press through the forcing machine solid feed inlet, further above-mentioned liquid-state epoxy resin (A1) is sent into to react in the forcing machine at follow-up liquid material charging opening near forcing machine solid materials charging opening more afterwards and extrudes; Can also be according to the needs of the finished product performance; Can optionally send into above-mentioned additive as other compositions, additive can directly be sent into forcing machine from feeding section behind the thorough mixing with above-mentioned material in premixed device, also can be in fusion transportation section input forcing machine; Last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation.
Above-mentioned epoxy resin (A) component is made up of liquid-state epoxy resin (A1) and solid epoxy resin (A2) among the present invention; Also can adopt the preparation method c2 of optimization; Comprise the steps: earlier composite solidifying agent of epoxy resin (B) and part solid epoxy resin (A2) through forcing machine or rotate the solid epoxy resin masterbatch that roller is prepared into the powdered epoxy composite curing agent, afterwards, again with the solid epoxy resin (A2) of rest part and composite solidifying agent of epoxy resin masterbatch through mixing tank with powdery uniform mixing each other; Preferably; Mixing tank has the temperature rise of chuck to avoid causing owing to friction that can lead to water coolant, afterwards, more mixed material is sent in the screw extrusion press through the forcing machine solid feed inlet; Afterwards; Further above-mentioned liquid-state epoxy resin (A1) is sent into to react in the forcing machine at follow-up liquid material charging opening near forcing machine solid materials charging opening again and extrude, can also can optionally send into above-mentioned additive according to the needs of the finished product performance as other compositions; Additive can directly be sent into forcing machine from feeding section behind the thorough mixing with above-mentioned material in premixed device; Also can be in fusion transportation section input forcing machine, last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation.
Epoxy composite of the present invention has distinct softening temperature; Good solubility and stablize the composition epoxy resin of the B scalariform attitude that can reach storage period more than a year, said composition be at tackiness agent, glass fiber reinforced plastics product; Carbon-fibre composite, there is application potential aspects such as coating and rigid foamed plastics.
Be with above-mentioned:
(a1), composition epoxy resin: be the composition epoxy resin that epoxy resin and epoxy curing agent is carried out the broken B scalariform attitude that forms of extrusion reaction postcooling in screw extrusion press; The reactive base of used epoxy curing agent is 0.1~3.0 with the equivalence ratio of the epoxy group(ing) of epoxy resin.
(a2), like (a1) described composition epoxy resin: described extrusion reaction comprises melting treatment that epoxy resin and epoxy curing agent are carried out and the mixing processing after the melting treatment; The charge temperature of said screw extrusion press is 0~60 ℃; The temperature of melting treatment is 60~180 ℃; Mixing treatment temperature is 100~200 ℃, and the drop temperature of screw extrusion press is 180~200 ℃.
(a3), like (a1) or (a2) described composition epoxy resin, the screw speed of said screw extrusion press is 20~300rmp, the mean residence time of material in screw extrusion press is 600~900s.
(a4), like (a1) or (a2) described composition epoxy resin: said epoxy resin and epoxy curing agent mix the back earlier and feed intake to screw extrusion press after evenly again in mixing tank.
(a5), like (a1) or (a2) described composition epoxy resin: described epoxy curing agent comprises component A and B component; Described component A is one or more formations in Dyhard RU 100/modification Dyhard RU 100 class solidifying agent, two Maleimide, the PHB, and B component is an aromatic amine curing agent; The reactive base of B component is 0.01~99 with the equivalence ratio of the reactive base of component A.
(a6), like (a5) described composition epoxy resin, the reactive base of said epoxy curing agent is 0.8~1.25 with the equivalence ratio of the epoxy group(ing) of epoxy resin; The reactive base of said B component is 0.5~2 with the equivalence ratio of the reactive base of component A.
(a7), like (a4) described composition epoxy resin; When said epoxy resin and epoxy curing agent mix in mixing tank; Also in this mixing tank, add additive, described additive is one or more formations in epoxy resin cure promotor, epoxide resin reactive diluent, epoxide resin reactive toughner, mineral filler, silane coupling agent, the tinting material.
Embodiment
Further specify the present invention below in conjunction with embodiment, but the scope of also unrestricted claim protection of the present invention adopts following testing method in an embodiment:
Epoxy resin component reaches the determination methods of B scalariform attitude: sample is poured in the xylene solvent, fully stirred and leave standstill the back if the layering turbid phenomenon occurs, show that then this reaction has arrived B scalariform attitude;
The determination methods of B scalariform attitude epoxy resin component stability: under the room temperature condition; The B scalariform attitude epoxy resin component sample that does not add mineral filler is deposited in the sealed vessel; Sampling regularly joins (for example acetone) in the epoxy resin good solvent; Stir afterwards, if the sample that takes out can be dissolved in the solvent fully and form homogeneous system, then interpret sample still has good stability.
The measuring method of epoxy composite softening temperature: adopt ring and the automatic softening temperature tester of ball measuring method as softening temperature.
Embodiment 1
The B scalariform attitude epoxy resin component proportioning of present embodiment sees the following form 1:
Table 1
The preparation method: under the normal temperature, under whipped state with epoxy resin DER331 and DER736,5; 5 '-dimethyl--4,4 '-diaminodiphenyl-methane and PHB add in the stirring tank, stir 3 hours to mixing; Keep then under the whipped state, adopting melt metering pump that mixture is sent to length-to-diameter ratio L/D is in 50 the twin screw extruder, 30 ℃ of screw extrusion press feeding section temperature; 100 ℃ of melt zone temperature, 150 ℃ of mixing conversion zone temperature, 180 ℃ of discharging section temperature; Screw speed will be controlled at 90rpm, and last material is extruded from the forcing machine discharging section, promptly obtains product through overcooling conveying and fragmentation; Products obtained therefrom can be stablized and reaches storage period more than 12 months, and softening temperature is 83 ℃.
Embodiment 2
The B scalariform attitude epoxy resin component solution synthetic ratio of present embodiment sees the following form 2:
Table 2
The preparation method: under the normal temperature, with epoxy resin E-21, mphenylenediamine and bismaleimides mix with powdery in the high speed pulverization mixing machine of band cooling water jecket; Using the solid feeding machine to send into length-to-diameter ratio L/D from the forcing machine solid feed inlet again is in 55 the twin screw extruder, adopts the viscosity measurement pump to be sent in the forcing machine from adjacent liquid charging opening CYDPG-207 again, 30 ℃ of screw extrusion press feeding section temperature; 120 ℃ of melt zone temperature; 150 ℃ of mixing conversion zone temperature, 180 ℃ of discharging section temperature, screw speed will be controlled at 110rpm; Last material is extruded from the forcing machine discharging section; Promptly obtain product through overcooling conveying and fragmentation, products obtained therefrom can be stablized and reaches storage period more than 12 months, and softening temperature is 85 ℃.
Embodiment 3
The B scalariform attitude epoxy resin component solution synthetic ratio of present embodiment sees the following form 3:
Table 3
The preparation method: under the normal temperature, with epoxy resin E-21, m-xylene diamine and Dyhard RU 100 join in the high speed pulverization mixing machine of being with cooling water jecket and mix with powdery; Using the solid feeding machine to send into length-to-diameter ratio L/D from the forcing machine solid feed inlet again is in 80 the twin screw extruder, 30 ℃ of screw extrusion press feeding section temperature, 120 ℃ of melt zone temperature; 170 ℃ of mixing conversion zone temperature, 180 ℃ of discharging section temperature, screw speed will be controlled at 120rpm; Last material is extruded from the forcing machine discharging section; Promptly obtain product through overcooling conveying and fragmentation, products obtained therefrom can be stablized and reaches storage period more than 12 months, and softening temperature is 87 ℃.