CN108250396A - A kind of environment protection type high-strength shock resistance moulding compound and preparation method thereof - Google Patents
A kind of environment protection type high-strength shock resistance moulding compound and preparation method thereof Download PDFInfo
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- CN108250396A CN108250396A CN201711495765.7A CN201711495765A CN108250396A CN 108250396 A CN108250396 A CN 108250396A CN 201711495765 A CN201711495765 A CN 201711495765A CN 108250396 A CN108250396 A CN 108250396A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08K7/14—Glass
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08L75/08—Polyurethanes from polyethers
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Abstract
The present invention provides a kind of polyurethane-epoxy resin and the moulding compound containing polyurethane-epoxy resin, the raw material of the polyurethane-epoxy resin are：Bisphenol A epoxide resin, poly- (tetramethylene copolymerization ethyleneether) glycol, 1,3 propylene glycol and diphenylmethylene diisocyanate.Meanwhile the present invention also provides the moulding compounds containing polyurethane-epoxy resin.Polyurethane-epoxy resin provided by the invention has many advantages, such as impact flexibility, and has with the moulding compound that other compositions are formed by it that fillibility is good, mobility is high, curing rate is fast, VOC free discharge.
Description
Technical field
The present invention relates to a kind of polymer composites, and in particular to a kind of environment protection type high-strength shock resistance moulding compound and its
Preparation method.
Background technology
Epoxy molding plastic (EMC-Epoxy Molding Compound) is using epoxy resin as matrix resin, adds in solid
Agent adds in filler, accelerating agent, fire retardant, colorant, coupling agent and other microcomponents, before passing through according to a certain percentage
Mixed, extrusion, magnetic separation, mixes crushing afterwards, and the techniques such as preforming are made.Its reaction mechanism is：By epoxy resin in epoxy mold materials
Binding agent is made, curing agent is weighed with other components, mixed, according to a certain percentage using single group prepared after hot mixing
Subassembly object, the epoxy ring-opening of epoxy resin chemically reacts under the action of heat and curing agent, generates crosslinking curing and makees
With thermosetting plastics is made, the epoxy molding plastic after curing has good caking property, and excellent electrical insulating property, machinery is by force
The features such as degree is high, and heat resistance and chemical resistance are good, and water absorption rate is low, and inprocess shrinkage is small, and building-up property is good.
In early days, it has been reported that the method with glass fiber reinforcement epoxy molding compound, i.e., is added in bisphenol A type epoxy resin solid
Agent (bottom crystalline substance eutectic mixed aromatic diamine), short glass fiber, silicon powder, stearic acid, titanium dioxide and dyestuff etc. are prepared into plain edition
Moulding compound, the moulding compound release property finally made is good, and molding is rapid, and resistance to cracking is good, and electric insulating quality is excellent.Wherein it is chopped
Glass fibre is alkali-free short glass fiber, is surface-treated by soluble epoxide, length 25-45mm, a diameter of 5-10
μ.(CN88105532.8, Publication No. 1038458A)
Later, many inventors other phenolic resin in epoxy molding plastic increased the property of moulding compound, in addition to using
Outside bisphenol A type epoxy resin, other epoxy resin are also added：
Blending epoxy system：Bisphenol A type epoxy resin, o-cresol linear phenolic epoxy resin or novolac epoxy resin
And brominated bisphenol a type epoxy resin, 45-95 parts, 0-48 parts, 5-24 parts are respectively accounted in 100 parts of blending epoxy systems
(CN96116343.7, Publication No. CN1150597A)；
Blending epoxy：100 parts by 60-90 parts of liquid diglycidyl ether type epoxy resin and solid bisphenol A type ring oxygen
10-40 parts of compositions (CN200710052683.5, Publication No. CN101096443A) of resin；
Epoxy resin and phenolic resin composition：Epoxy resin and phenolic resin weight part are respectively 20-25 parts, 7-9 parts, institute
State (CN200810124670.9, Publication No. CN101343398A) that phenolic resin is acid system production
Epoxy resin and modified epoxy resin：100 parts of modified epoxy, 0-100 parts of epoxy resin, wherein modified ring
Oxygen resin is the mixture of epoxy resin and liquid rubber, 83-95 parts of epoxy resin, 5-17 parts of liquid rubber.
(CN201110274707.8, Publication No. CN102321340A)
The combination of polyurethane modified epoxy resin and phenolic resin：Polyurethane modified epoxy resin 10-80, phenolic resin 5-
12nd, polysulfide rubber 1-10, polypropylene glycol diglycidyl ether 0.01-1, curing agent 5-60, thixotropic agent 1-8, compound accelerant
0.1-3, coupling agent 1-6, the polyurethane modified epoxy resin consist of the following compositions, bisphenol A epoxide resin 60-120, polyester
Polyalcohol 10-40, methyl diphenylene diisocyanate 4-7,1,4- butanediol 0.5-2, dihydroxy methylpropane 0.1-2
(CN201410529459.0, Publication No. CN104531034A)
As seen from the above, epoxy resin is added in moulding compound raw material, is a kind of method for improving moulding compound.
Epoxy resin is a kind of important thermosetting resin, is had a wide range of applications in field of compound material.Bisphenol-A type ring
Oxygen resin is most conventional epoxy resin, has good comprehensive performance, but unmodified system is difficult to meet high tenacity requirement.Fat
Ring race epoxy resin has excellent mechanical performance, electrical insulation capability, chemical stability, high and low temperature resistance and weather-proof etc.
Advantage.Not only there is the characteristic of epoxy resin through polyurethane-modified epoxy resin but also to remain polyurethane flexibility good,
Particularly excellent performance is had more through Molecular Design polyurethane-epoxy resin.
The polyurethane modified epoxy resin consists of the following compositions, bisphenol A epoxide resin 60-120, polyester polyol
10-40, methyl diphenylene diisocyanate 4-7,1,4- butanediol 0.5-2, dihydroxy methylpropane 0.1-2
(CN201410529459.0, Publication No. CN104531034A), but when the product is prepared into moulding compound, flexibility is still
Can, the performances such as rigidity are insufficient.
In general, moulding compound in order to increase the wellability of the inorganic material such as resin and filler, fiber, uses the dilution of low viscosity
Agent.Process of manufacture can generate volatile matter, not only influence environment, if the improper body that can also influence operator of protection is good for
Health.With the promotion of national requirements for environmental protection, such product will have become increasingly limited.
At present, lack the moulding compound that the feature of environmental protection is good, high mechanical strength and shock resistance are good in the market, and this is electricity
Son encapsulation, insulation etc. industries there is an urgent need to.Therefore, environment protection type high-strength shock resistance moulding compound just seems particularly urgently and again
It will.
Invention content
The first object of the present invention is to provide a kind of polyurethane-epoxy resin, and the raw material of the polyurethane-epoxy resin is：It is double
Phenol A epoxy resin, poly- (tetramethylene-copolymerization-ethyleneether) glycol, 1,3- propylene glycol and diphenylmethylene diisocyanate
Ester.
Specifically, the raw material of the polyurethane-epoxy resin contains the ingredient of following parts by weight：Bisphenol A epoxide resin 100
Part, poly- (tetramethylene-copolymerization-ethyleneether) 10~35 parts of glycol, 2~4 parts of 1,3- propylene glycol, two isocyanide of diphenylmethylene
10~20 parts of acid esters.
Preferably, the raw material of the polyurethane-epoxy resin contains the ingredient of following parts by weight：Bisphenol A epoxide resin 100
Part, poly- (tetramethylene-copolymerization-ethyleneether) 25~35 parts of glycol, 2~3 parts of 1,3- propylene glycol, two isocyanide of diphenylmethylene
10~20 parts of acid esters.
Further preferably, the raw material of the polyurethane-epoxy resin contains the ingredient of following parts by weight：Bisphenol A epoxide resin
100 parts, poly- (tetramethylene-copolymerization-ethyleneether) 25~30 parts of glycol, 2~3 parts of 1,3- propylene glycol, diphenylmethylene two
15~20 parts of isocyanates.
The present invention also provides the preparation method of above-mentioned polyurethane-epoxy resin, this method includes the following steps：By raw material
Pretreatment is to water content 0.2wt% hereinafter, by poly- (tetramethylene-copolymerization-ethyleneether) glycol, two isocyanide of diphenylmethylene
Acid esters mixes, and is heated to 65~85 DEG C, reacts 1~4 hour under nitrogen protection, 1,3-PD is added in, in 70-95 DEG C of nitrogen
The reaction was continued under gas shielded 1~4 hour, obtains polyurethane prepolymer, then by polyurethane prepolymer and bisphenol A epoxide resin,
It is heated to 65~85 DEG C of 1~3 hours of reaction under nitrogen protection to get polyurethane-epoxy resin.
Another object of the present invention is to provide a kind of moulding compound prepared by above-mentioned polyurethane-epoxy resin.
A kind of environment protection type high-strength shock resistance moulding compound, raw material contain the ingredient of following mass parts：Bisphenol A type epoxy resin
100 parts, 10~35 parts of polyurethane-epoxy resin, 30~60 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, ring
10~20 parts of oxygen curing agent, 1~3 part of epoxy accelerating agent, Al2O3100~200 parts, 0.2-0.5 parts of coupling agent containing epoxy group and
50~100 parts of chopped reinforcing fibers.
Preferably, the moulding compound is made of the ingredient of following mass parts：100 parts of bisphenol A type epoxy resin, polyurethane rings
20~30 parts of oxygen resin, 45~60 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, epoxy hardener 12~18
Part, 1.5~3 parts of epoxy accelerating agent, Al2O3130~200 parts, 0.2-0.5 parts of coupling agent containing epoxy group and chopped reinforcing fibers
50~70 parts.
Further preferably, the moulding compound is made of the ingredient of following mass parts：100 parts of bisphenol A type epoxy resin, poly- ammonia
24~30 parts of ester epoxy resin, 50~60 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, epoxy hardener 15
~18 parts, 2~3 parts of epoxy accelerating agent, Al2O3130~200 parts, 0.2~0.5 part of coupling agent containing epoxy group and the enhancing that is chopped
60~70 parts of fiber.
In above-mentioned moulding compound raw material：
The epoxy hardener is alkaline epoxy hardener, and specially aliphatic diamine, polyamines, aromatic polyamine, double cyanogen is double
Amine, imidazoles, modified amine, preferably dicyandiamide, preferably micron order dicyandiamide, further preferably grain size are 5-30
μm dicyandiamide.
The epoxy accelerating agent is imidazoles, and specially 2-methylimidazole, 2- ethyl -4- methyl narrows azoles, further preferably
For 2-ethyl-4-methylimidazole.
The chopped reinforcing fibers are the carbon fiber of the glass fibre of 6-20mm, 6-12mm.
The coupling agent containing epoxy group is KH560 coupling agents.
The present invention also provides the preparation methods of moulding compound, include the following steps：According to proportioning, weigh epoxy resin, gather
Urethane epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, are heated to 100~120 DEG C, kneader side
It stirs side and adds in epoxy hardener, stir 30~60min, then add in Al2O3With coupling agent containing epoxy group, it is sufficiently stirred
It is even, then add in enhanced short fiber stirring combine 5-10min to get.
Moulding compound provided by the invention has the following advantages：
1st, polyurethane-epoxy resin provided by the invention：
Polyurethane is also a major class product in itself, and Various Functions are all much according to performance requirement design structure, in order to increase
Add the rigid, flexible of epoxy resin, flexibility, inventor has found that methylene based structures can be introduced in its structure, in order to select
Appropriate raw material, inventor have found by a large amount of experiment：Using-one diethyl acetal esterdiol of polyadipate ethylene glycol, it is made
Product it is soft but intensity is low, too fast using reaction speed during diglycol, reaction is easily out of control, final to determine using double
Phenol A types epoxy resin, poly- (tetramethylene-copolymerization-ethyleneether) glycol, 1,3- propylene glycol and diphenylmethylene diisocyanate
Ester prepares polyurethane-epoxy resin.
It is compared, this hair with CN104531034A (application No. is CN201410529459.0, hereinafter referred to as patent in 2014)
The polyurethane-epoxy resin of bright preparation has following difference：
Reaction principle：All it is first synthesis of polyurethane performed polymer, then reacts to form polyurethane-epoxy resin with epoxy resin；
On raw material：The raw material that patent in 2014 uses is bisphenol A epoxide resin, polyester polyol, diphenyl methane two
Isocyanates, 1,4- butanediols, dihydroxy methylpropane.
The raw material that the present invention uses is bisphenol A type epoxy resin, poly- (tetramethylene-copolymerization-ethyleneether) glycol, 1,3-
Propylene glycol and diphenylmethylene diisocyanate；
It is well known that when preparing polyurethane-epoxy resin, molecule segment is longer in raw material, and product flexibility is better,
But nor the longer the better, raw material strand is long to lead to some negative effects, for example product flexibility is good, but strong
Degree declines, therefore selects poly- (tetramethylene-copolymerization-ethyleneether) glycol.
Diphenylmethylene diisocyanate, than methyl diphenylene diisocyanate in structure more methylene, anti-
At once, methylene can be present in the even final polyurethane-epoxy resin of prepolymer, and the product flexibility finally prepared is more preferable.
Patent in 2014 does not mention which kind of polyalcohol is polyester polyol be, and poly- (tetramethylene-copolymerization-ethyleneether) two
Alcohol, than conventional polyester polyol in structure more methylene, in reaction, it is even final that methylene can be present in prepolymer
In polyurethane-epoxy resin, the product rigidity and toughness finally prepared is more preferable.
On product：Polyurethane epoxy increases long methylene group, comprehensive poly- (tetramethylene-copolymerization-Asia in structure
Ethylether) glycol flexibility and diphenylmethylene diisocyanate in rigidity and toughness, impart polyurethane epoxy
The better impact flexibility of resin.
2nd, moulding compound provided by the present invention, raw material have：
Polyurethane-epoxy resin used is voluntarily to prepare, and specific molecular chain structure assigns the better impact flexibility of system；
4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters are to contain 1 alicyclic epoxy in a kind of molecular structure
3 energy degree epoxy resin of base and 2 glycidol ester groups have the double grading of alicyclic epoxy and ethylene oxidic ester, the tree concurrently
The comprehensive performance of fat is preferable, and functional group and crosslink density increase do not make brittleness significantly increase, and rigidity is relatively good with toughness.
Its solidfied material has the characteristics that high temperature resistant, high intensity, high adhesiveness, and weatherability, lower temperature resistance and electrical insulating property are also fine.
Epoxy hardener used is alkaline epoxy hardener, preferably dicyandiamide, particularly 5-30 μm of dicyandiamide
Effect is best in an experiment, and 5-30 μm of dicyandiamide and epoxy resin compatibility are more preferable, curing reaction speed faster, solidfied material machine
Tool performance higher；
Epoxy accelerating agent used can promote curing efficiency, reduce solidification temperature and take into account system Storage period simultaneously；
This curing agent/accelerator system has latency, and the storage stability for making moulding compound is good, and usage amount should be
Too low in above range of the present invention, then system curing is insufficient, will reduce the performance of resin；It is excessively high, then not only influence moulding compound
Performance also influences storage stability.
Coupling agent containing epoxy group used can improve resin and inorganic material interface；
By above-mentioned raw materials prepare moulding compound, have fillibility is good, mobility is high, curing rate is fast, VOC free discharge it is excellent
Point.There is high mechanical strength, temperature resistant grade is high, excellent in cushion effect, water absorption rate is low etc. after the mold compound curing processing of gained simultaneously
Advantage.In general, gained moulding compound is added in 160~180 DEG C of mold, cures 10~30min, be cooled to room temperature i.e. plastic.
3rd, compared with prior art patent in 2014, moulding compound provided by the invention has following difference：
1) on raw material：
Three kinds of resins share：Patent in 2014 is combined using polyurethane modified epoxy resin, phenolic resin and polysulfide rubber,
The present invention is shunk using bisphenol A epoxide resin, polyurethane modified epoxy resin and 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two
Glyceride, first, the polyurethane-epoxy resin flexibility that polyurethane-epoxy resin of the present invention was provided compared with 2014 are more preferable, and with gathering
Sulphur rubber is compared, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, has preferably rigidity, intensity and heat resistance
It can energy.It is more preferable that bisphenol A epoxide resin of the present invention compares the phenolic resin comprehensive performance provided in 2014.
2) curing agent：
Patent in 2014 is used using dimethyl amine propylamine, diethylamine propylamine, beta-hydroxyethyl ethylenediamine, the present invention
Be dicyandiamide, and the micron order dicyandiamide that preferable particle size is 5-30 μm, be solid first under dicyandiamide room temperature, compare
Year in 2014, patent liquid amine organic volatile was low, had better environmental-protecting performance, sub-micron grade dicyandiamide cured epoxy
Compared to 2014 patents of resin have higher intensity and heat resistance.
3) accelerating agent：
Patent in 2014 uses the combination of compound accelerant, i.e. dicyandiamide and imidazoles, and the present invention selects 2- ethyls -4-
Methylimidazole cooperation curing agent micron order dicyandiamide assigns moulding compound low temperature latency and high temperature rapid curing processability.Compared with
The prior art is compared, and moulding compound provided by the invention has the advantages such as fillibility is good, mobility is high, curing rate is fast, curing
Object has the advantages that high mechanical strength, temperature resistant grade are high, excellent in cushion effect, water absorption rate is low etc..
4th, the present invention has the advantages that：
1) present invention is ensured by the polyurethane-type epoxy resin for introducing alicyclic epoxy and synthesizing, moulding compound obtained
Its excellent shock resistance, bending property, anti-stress cracking performance and heat resistance；
2) for the present invention by optimizing micron order dicyandiamide/modified imidazole, it is good that curing/promotion system ensures that moulding compound has
Storage stability and high temperature rapid curing processability.
Specific embodiment
With reference to embodiment, the present invention will be described in detail.
Embodiment 1：A kind of polyurethane-epoxy resin and its preparation
1st, raw material：Bisphenol A epoxide resin 100g, poly- (tetramethylene-copolymerization-ethyleneether) glycol 25g, diphenyl methylene
Group diisocyanate 15g, 1,3- propylene glycol 3g.
2nd, preparation method：
Poly- (tetramethylene-copolymerization-ethyleneether) glycol, diphenylmethylene diisocyanate are weighed according to proportioning, is added
Heat reacts 2.5 hours under nitrogen protection to 75 DEG C.Then 1,3-PD is added in, is continued in the case where 85 DEG C of nitrogen are protected anti-
2 hours are answered, obtain polyurethane prepolymer.Bisphenol A epoxide resin is added in polyurethane prepolymer, 70 DEG C are heated to, in nitrogen
Protection lower 3 hours of reaction, obtain polyurethane-epoxy resin.
Embodiment 2：A kind of polyurethane-epoxy resin and its preparation
1st, raw material：Bisphenol A epoxide resin 100g, poly- (tetramethylene-copolymerization-ethyleneether) glycol 30g, diphenyl methylene
Group diisocyanate 20g, 1,3- propylene glycol 2g.
2nd, preparation method：Poly- (tetramethylene-copolymerization-ethyleneether) glycol, diphenylmethylene two are weighed according to proportioning
Isocyanates is heated to 80 DEG C, reacts 2 hours under nitrogen protection.Then 1,3-PD is added in, is protected in 85 DEG C of nitrogen
The reaction was continued down 2 hours, obtains polyurethane prepolymer.Bisphenol A epoxide resin is added in polyurethane prepolymer, is heated to 70
DEG C, 3 hours are reacted under nitrogen protection, obtain polyurethane-epoxy resin.
Embodiment 3：A kind of polyurethane-epoxy resin and its preparation
1st, raw material：Bisphenol A epoxide resin 100g, poly- (tetramethylene-copolymerization-ethyleneether) glycol 25g, diphenyl methylene
Group diisocyanate 10g, 1,3- propylene glycol 2g.
2nd, preparation method：Poly- (tetramethylene-copolymerization-ethyleneether) glycol, diphenylmethylene two are weighed according to proportioning
Isocyanates is heated to 75 DEG C, reacts 2 hours under nitrogen protection.Then 1,3-PD is added in, is protected in 90 DEG C of nitrogen
The reaction was continued down 1 hour, obtains polyurethane prepolymer.Bisphenol A epoxide resin is added in polyurethane prepolymer, is heated to 80
DEG C, 2 hours are reacted under nitrogen protection, obtain polyurethane-epoxy resin.
Embodiment 4：A kind of polyurethane-epoxy resin and its preparation
1st, raw material：Bisphenol A epoxide resin 100g, poly- (tetramethylene-copolymerization-ethyleneether) glycol 35g, diphenyl methylene
Group diisocyanate 12g, 1,3- propylene glycol 3g.
2nd, preparation method：
Poly- (tetramethylene-copolymerization-ethyleneether) glycol, diphenylmethylene diisocyanate are weighed according to proportioning, is added
Heat reacts 3 hours under nitrogen protection to 70 DEG C.Then 1,3-PD is added in, the reaction was continued in the case where 80 DEG C of nitrogen are protected 3
A hour, obtain polyurethane prepolymer.Bisphenol A epoxide resin is added in polyurethane prepolymer, is heated to 85 DEG C, is protected in nitrogen
1.5 hours of lower reaction, obtain polyurethane-epoxy resin.
Experimental example 1：The comparison of impact flexibility
1st, experiment packet：Polyurethane-epoxy resin prepared by embodiment 1-4, comparative example 1, with reference to the reality in patent in 2014
Polyurethane-epoxy resin prepared by the method for applying example 1 (CN104531034A, application No. is CN201410529459.0).
2nd, experimental method：The polyurethane-epoxy resin of metering is placed in beaker, is heated to 80-100 DEG C, adds in the double cyanogen of micron
Diamine, 2-ethyl-4-methylimidazole stir evenly, and preheated mold is poured into after vacuum defoamation.Cure 1h at 160 DEG C.It prepares
Sample presses the measure part 1 of GB/T1043.1-2008 plastics Charpy Impact performances：Non-instrument impact test testing program
Carry out impact flexibility test；GBT9341 Plastics-Oetermination of flexural properties method carries out bending strength test.
3rd, experimental result：It is shown in Table 1
Table 1：The performance of embodiment 1-4 and comparative example gained polyurethane-epoxy resin
Table 1 the results show that the impact strength of embodiment 1,2,4 better than comparative example, the bending strength of embodiment 1,2 is better than pair
Ratio, although the bending strength of embodiment 3,4 is suitable with comparative example, impact strength is slightly better than comparative example, so embodiment 3
Impact flexibility with 4 is good.With 2 best results of embodiment in terms of impact flexibility.
The result shows that the present invention prepares polyurethane resin with better toughness.
Embodiment 5：A kind of environment protection type high-strength shock resistance moulding compound
1st, raw material：
Bisphenol A epoxide resin 100g, polyurethane-epoxy resin (are prepared) 20g, 4,5- 7-oxa-bicyclo[4.1.0-1 by embodiment 1,
2- dicarboxylic acid diglycidyl esters 45g, 5 μm of dicyandiamide 12g, 2-ethyl-4-methylimidazole 1.5g, Al2O3 150g、KH560
Coupling agent 0.25g, 12mm glass fibre 60g.
2nd, preparation method：
Bisphenol A epoxide resin, polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two are weighed according to raw material
Ethylene oxidic ester is mixed and heated to 110 DEG C, after being sufficiently stirred, and stirring adds in curing agent, and accelerating agent is stirred to react 30min, adds
Enter Al2O3It is stirred with KH560 coupling agents, adds in glass fibre, mediate 8min.By obtained moulding compound in 170 DEG C of moulds
Press curing 15min in tool.
Embodiment 6：A kind of environment protection type high-strength shock resistance moulding compound
1st, raw material：Bisphenol A epoxide resin 100g, polyurethane-epoxy resin (are prepared) 30g, 4,5- epoxide ring by embodiment 3
Hexane -1,2- dicarboxylic acid diglycidyl esters 50g, 10 microns of dicyandiamide 15g, 2-ethyl-4-methylimidazole 2g,
Al2O3180g, KH560 coupling agent 0.45g, 12mm carbon fiber 50g.
2nd, preparation method：
Bisphenol A epoxide resin, polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two are weighed according to raw material
Ethylene oxidic ester is mixed and heated to 100 DEG C, after being sufficiently stirred, and stirring adds in curing agent, and accelerating agent is stirred to react 30min, adds
Enter Al2O3It is stirred with KH560 coupling agents, adds in carbon fiber, mediate 10min.By obtained moulding compound in 180 DEG C of moulds
Press curing 5min in tool.
Embodiment 7：A kind of environment protection type high-strength shock resistance moulding compound
1st, raw material：Bisphenol A epoxide resin 100g, polyurethane-epoxy resin (are prepared) 25g, 4,5- epoxide ring by embodiment 1
Hexane -1,2- dicarboxylic acid diglycidyl esters 60g, 20 μm of dicyandiamide 18g, 2-ethyl-4-methylimidazole 2.5g,
Al2O3200g, KH560 coupling agent 0.5g, 20mm glass fibre 50g, 12mm carbon fiber 20g.
2nd, preparation method：
Bisphenol A epoxide resin, polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two are weighed according to raw material
Ethylene oxidic ester is mixed and heated to 100 DEG C, after being sufficiently stirred, and stirring adds in curing agent, accelerating agent, is stirred to react 30min, adds
Enter Al2O3It is stirred with KH560 coupling agents, adds in glass fibre, carbon fiber, mediate 10min.The moulding compound that will be obtained
The press curing 10min in 175 DEG C of molds.
Embodiment 8：A kind of environment protection type high-strength shock resistance moulding compound
1st, raw material：Bisphenol A epoxide resin 100g, polyurethane-epoxy resin (are prepared) 24g, 4,5- epoxide ring by embodiment 2
Hexane -1,2- dicarboxylic acid diglycidyl esters 52g, 30 microns of dicyandiamide 15g, imidazole curing agent 3g, Al2O3 130g、
KH560 coupling agent 0.2g, 12mm carbon fiber 50g, 6mm glass fibres 20g.
2nd, preparation method：
Bisphenol A epoxide resin, polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two are weighed according to raw material
Ethylene oxidic ester is mixed and heated to 110 DEG C, after being sufficiently stirred, and stirring adds in curing agent, and accelerating agent is stirred to react 30min, adds
Enter Al2O3It is stirred with KH560 coupling agents, adds in carbon fiber, glass fibre, mediate 10min, the moulding compound that will be obtained
The press curing 15min in 165 DEG C of molds.
Comparative example 1：(the conventional moulding compound of synthesis of polyurethane epoxy resin and micron order dicyandiamide in invention is not used)
Common moulding compound：Bisphenol A epoxide resin 100g is weighed, is mixed and heated to 100 DEG C, after being sufficiently stirred, stirring adds in
Common dicyandiamide 20g, is stirred to react 30min, adds in Al2O3120g is stirred, and adds in 12mm glass fibre 80g, is mediated
10min.By obtained moulding compound in 185 DEG C of molds press curing 15min.
Comparative example 2：With reference to the embodiment 1 in CN104531034A (application No. is CN201410529459.0) patent application
The moulding compound being prepared.
Experimental example 5-8 performance tests：
1st, laboratory sample：Moulding compound prepared by embodiment 5-8, moulding compound prepared by comparative example 1,2.
2nd, detection method：
GBT1451-2005 (National Standard of the People's Republic of China) fibre reinforced plastics freely-supported beam type impact flexibility；
GBT1449-2005 (National Standard of the People's Republic of China) fibre reinforced plastics bending property test method；
Glass transition temperature, test equipment produce differential scanning calorimeter (DSC) for Nai Chi companies, and test temperature is
30-250 DEG C, 5 DEG C/min of heating rate.
3rd, experimental result：It is shown in Table 2
Table 2：The performance of embodiment 5-8 and comparative example gained moulding compound
2 result of table is shown：Embodiment 5-8 is superior to comparative example 1 in terms of impact flexibility and bending property, wherein impacting tough
Property, in terms of bending property, embodiment 6-8 effects are more preferable, even more better than comparative example 1 and comparative example 2.
The result shows that moulding compound provided by the invention is the strong moulding compound of a kind of environment-friendly type, high intensity, impact resistance.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, the ordinary skill people of fields
Member, which should be appreciated that, can be modified or replaced equivalently the specific embodiment of the present invention with reference to above-described embodiment, these
Without departing from any modification of spirit and scope of the invention or equivalent replacement apply pending claims it
It is interior.
Claims (10)
1. a kind of polyurethane-epoxy resin, the raw material of the polyurethane-epoxy resin are：Bisphenol A epoxide resin, it is poly- (tetramethylene-
Copolymerization-ethyleneether) glycol, 1,3- propylene glycol and diphenylmethylene diisocyanate.
2. according to the polyurethane-epoxy resin described in claims 1, which is characterized in that the raw material of the polyurethane-epoxy resin
Ingredient containing following parts by weight：100 parts of bisphenol A epoxide resin, poly- (tetramethylene-copolymerization-ethyleneether) glycol 10~35
Part, 2~4 parts of 1,3- propylene glycol, 10~20 parts of diphenylmethylene diisocyanate.
3. according to the polyurethane-epoxy resin described in claims 2, which is characterized in that the raw material of the polyurethane-epoxy resin
Ingredient containing following parts by weight：100 parts of bisphenol A epoxide resin, poly- (tetramethylene-copolymerization-ethyleneether) glycol 25~35
Part, 2~3 parts of 1,3- propylene glycol, 10~20 parts of diphenylmethylene diisocyanate；
Preferably, the raw material of the polyurethane-epoxy resin contains the ingredient of following parts by weight：100 parts of bisphenol A epoxide resin gathers
(tetramethylene-copolymerization-ethyleneether) 25~30 parts of glycol, 2~3 parts of 1,3- propylene glycol, diphenylmethylene diisocyanate
15~20 parts.
4. a kind of preparation method of polyurethane-epoxy resin, this method include the following steps：By any one of claims 1-3 institutes
Pretreatment of raw material is stated to water content 0.2wt% hereinafter, by poly- (tetramethylene-copolymerization-ethyleneether) glycol, diphenylmethylene
Diisocyanate mixes, and is heated to 65~85 DEG C, reacts 1~4 hour under nitrogen protection, 1,3-PD is added in, in 70-
The reaction was continued under 95 DEG C of nitrogen protections 1~4 hour, polyurethane prepolymer is obtained, then by polyurethane prepolymer and bisphenol-A epoxy
Resin is heated to 65~85 DEG C of 1~3 hours of reaction to get polyurethane-epoxy resin under nitrogen protection.
5. a kind of moulding compound, raw material contains the ingredient of following mass parts：100 parts of bisphenol A type epoxy resin, claims 1-
3 10~35 parts of any one of them polyurethane-epoxy resins, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters 30~
60 parts, 10~20 parts of epoxy hardener, 1~3 part of epoxy accelerating agent, Al2O3100~200 parts, the 0.2- of coupling agent containing epoxy group
0.5 part and 50~100 parts of chopped reinforcing fibers.
6. according to the moulding compound described in claims 5, which is characterized in that the moulding compound by following mass parts ingredient system
Into：100 parts of bisphenol A type epoxy resin, 20~30 parts of polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two contract
45~60 parts of water glyceride, 12~18 parts of epoxy hardener, 1.5~3 parts of epoxy accelerating agent, Al2O3130~200 parts, containing epoxy
50~70 parts of 0.2-0.5 parts of group coupling agent and chopped reinforcing fibers；
Preferably, the moulding compound is made of the ingredient of following mass parts：100 parts of bisphenol A type epoxy resin, polyurethane epoxy tree
24~30 parts of fat, 50~60 parts of 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, 15~18 parts of epoxy hardener,
2~3 parts of epoxy accelerating agent, Al2O3130~200 parts, 0.2~0.5 part of coupling agent containing epoxy group and chopped reinforcing fibers 60~
70 parts.
7. the moulding compound according to claims 5 or 6, which is characterized in that the epoxy hardener is alkaline curable epoxide
Agent, specially aliphatic diamine, polyamines, aromatic polyamine, dicyandiamide, imidazoles, modified amine.
8. according to the moulding compound described in claims 7, which is characterized in that the epoxy hardener is dicyandiamide, preferably
Grain size is 5-30 μm of dicyandiamide.
9. the moulding compound according to claims 5 or 6, which is characterized in that the epoxy accelerating agent is imidazoles, specially
2-methylimidazole, 2- ethyl -4- methyl narrow azoles, further preferably 2-ethyl-4-methylimidazole；
The chopped reinforcing fibers are the carbon fiber of the glass fibre of 6-20mm, 6-12mm；
The coupling agent containing epoxy group is KH560 coupling agents.
10. a kind of preparation method of moulding compound, which is characterized in that include the following steps：According to any one of claims 5-9 institutes
The proportioning stated weighs epoxy resin, polyurethane-epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, adds
For heat to 100~120 DEG C, kneader adds in epoxy hardener while stirring, stirs 30~60min, then adds in Al2O3With containing ring
Oxygen groups coupling agent, stirs, then add in enhanced short fiber stirring mediate 5-10min to get.
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| CN112961459A (en) * | 2021-02-02 | 2021-06-15 | 中车青岛四方机车车辆股份有限公司 | Repairing material and repairing method |
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