CN108250396B - Environment-friendly high-strength impact-resistant molding compound and preparation method thereof - Google Patents
Environment-friendly high-strength impact-resistant molding compound and preparation method thereof Download PDFInfo
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- CN108250396B CN108250396B CN201711495765.7A CN201711495765A CN108250396B CN 108250396 B CN108250396 B CN 108250396B CN 201711495765 A CN201711495765 A CN 201711495765A CN 108250396 B CN108250396 B CN 108250396B
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
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- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- 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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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
The invention provides polyurethane epoxy resin and a molding compound containing the same, wherein the polyurethane epoxy resin comprises the following raw materials: bisphenol a epoxy resin, poly (tetramethylene-co-ethyleneether) glycol, 1, 3-propanediol, and diphenylmethylene diisocyanate. Meanwhile, the invention also provides a molding compound containing the polyurethane epoxy resin. The polyurethane epoxy resin provided by the invention has impact toughness, and the molding compound formed by the polyurethane epoxy resin and other components has the advantages of good filling property, high fluidity, high curing speed, no VOC (volatile organic compound) emission and the like.
Description
Technical Field
The invention relates to a polymer composite material, in particular to an environment-friendly high-strength impact-resistant molding compound and a preparation method thereof.
Background
The Epoxy Molding Compound (EMC-Epoxy Molding Compound) is prepared by taking Epoxy resin as matrix resin, adding a curing agent, adding a filler, an accelerator, a flame retardant, a coloring agent, a coupling agent and other trace components, and carrying out processes of pre-mixing, extruding, crushing, magnetic separation, post-mixing, preforming and the like according to a certain proportion. The reaction mechanism is as follows: the epoxy molding material is a single-component composition prepared by weighing, mixing and thermally mixing epoxy resin serving as a binder and a curing agent with other components according to a certain proportion, epoxy groups of the epoxy resin are subjected to ring opening chemical reaction under the action of heat and the curing agent to generate a crosslinking curing effect so as to form thermosetting plastic, and the cured epoxy molding material has the characteristics of good cohesiveness, excellent electrical insulation, high mechanical strength, good heat resistance and chemical corrosion resistance, low water absorption, small molding shrinkage, good molding process performance and the like.
In the early days, there was reported a method of reinforcing epoxy molding compound with glass fiber, i.e. adding curing agent (primary crystal eutectic mixed arylamine), short glass fiber, silica powder, stearic acid, titanium dioxide and dye into bisphenol A type epoxy resin to prepare common molding compound, the final molding compound has good demoulding property, rapid forming, good crack resistance and excellent electrical insulation property. Wherein the chopped glass fiber is alkali-free chopped glass fiber, is subjected to surface treatment by water-soluble epoxy, and has a length of 25-45mm and a diameter of 5-10 mu. (CN88105532.8, publication No. 1038458A)
Later, many inventors added other phenolic resins to epoxy molding compounds to increase the properties of the molding compounds, in addition to bisphenol a type epoxy resins:
mixed epoxy resin system: 45-95 parts of bisphenol A epoxy resin, 0-48 parts of o-cresol novolac epoxy resin or novolac epoxy resin and 5-24 parts of brominated bisphenol A epoxy resin in 100 parts of mixed epoxy resin system (CN96116343.7, publication number is CN 1150597A);
mixing epoxy resin: 100 parts of liquid glycidyl ether type epoxy resin 60-90 parts and solid bisphenol A type epoxy resin 10-40 parts (CN200710052683.5, publication number is CN 101096443A);
epoxy resin and phenolic resin combination: the weight parts of the epoxy resin and the phenolic resin are respectively 20-25 parts and 7-9 parts, and the phenolic resin is produced by an acid method (CN200810124670.9, publication number is CN101343398A)
Epoxy resin and modified epoxy resin: 100 parts of modified epoxy resin and 0-100 parts of epoxy resin, wherein the modified epoxy resin is a mixture of the epoxy resin and liquid rubber, 83-95 parts of the epoxy resin and 5-17 parts of the liquid rubber. (CN201110274707.8, publication No. CN102321340A)
Combination of polyurethane modified epoxy resin and phenolic resin: 10-80 parts of polyurethane modified epoxy resin, 5-12 parts of phenolic resin, 1-10 parts of polysulfide rubber, 0.01-1 part of polypropylene glycol diglycidyl ether, 5-60 parts of curing agent, 1-8 parts of thixotropic agent, 0.1-3 parts of composite accelerator and 1-6 parts of coupling agent, wherein the polyurethane modified epoxy resin comprises 60-120 parts of bisphenol A epoxy resin, 10-40 parts of polyester polyol, 4-7 parts of diphenylmethane diisocyanate, 0.5-2 parts of 1, 4-butanediol and 0.1-2 parts of dimethylolpropane (CN201410529459.0, publication number is CN104531034A)
From the above, it can be seen that the addition of epoxy resin to the raw material of the molding compound is a method for improving the molding compound.
Epoxy resins are an important class of thermosetting resins and have wide applications in the field of composite materials. Bisphenol a type epoxy resins are the most common epoxy resins and have good overall properties, but unmodified systems have difficulty meeting high toughness requirements. The alicyclic epoxy resin has the advantages of excellent mechanical property, electric insulation property, chemical stability, high and low temperature resistance, weather resistance and the like. The epoxy resin modified by polyurethane not only has the characteristics of epoxy resin, but also keeps the advantage of good flexibility of polyurethane, and particularly, the polyurethane epoxy resin has excellent performance through molecular structure design.
The polyurethane modified epoxy resin comprises 60-120 parts of bisphenol A epoxy resin, 10-40 parts of polyester polyol, 4-7 parts of diphenylmethane diisocyanate, 0.5-2 parts of 1, 4-butanediol and 0.1-2 parts of dimethylolpropane (CN201410529459.0, publication number is CN104531034A), but when the product is prepared into molding plastics, the product has the defects of sufficient flexibility, insufficient rigidity and the like.
In general, a low-viscosity diluent is used for a molding compound in order to increase wettability of a resin with an inorganic material such as a filler or a fiber. Volatile matters are generated in the production process, so that the environment is influenced, and the physical health of operators is also influenced if the protection is improper. With the increase of national environmental protection requirements, such products will be increasingly limited.
At present, molding compounds with good environmental protection, high mechanical strength and good impact resistance are lacked in the market, which is urgently needed in the industries of electronic packaging, insulation and the like. Therefore, the environmental protection type high-strength impact-resistant molding compound is urgent and important.
Disclosure of Invention
The first purpose of the invention is to provide a polyurethane epoxy resin, which comprises the following raw materials: bisphenol a epoxy resin, poly (tetramethylene-co-ethyleneether) glycol, 1, 3-propanediol, and diphenylmethylene diisocyanate.
Specifically, the raw materials of the polyurethane epoxy resin comprise the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 10-35 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-4 parts of 1, 3-propylene glycol and 10-20 parts of diphenylmethylene diisocyanate.
Preferably, the raw materials of the polyurethane epoxy resin comprise the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 25-35 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-3 parts of 1, 3-propylene glycol and 10-20 parts of diphenylmethylene diisocyanate.
More preferably, the raw materials of the polyurethane epoxy resin comprise the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 25-30 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-3 parts of 1, 3-propylene glycol and 15-20 parts of diphenylmethylene diisocyanate.
The invention also provides a preparation method of the polyurethane epoxy resin, which comprises the following steps: pretreating raw materials to the water content of below 0.2wt%, mixing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate, heating to 65-85 ℃, reacting for 1-4 hours under the protection of nitrogen, adding 1, 3-propylene glycol, continuing to react for 1-4 hours under the protection of nitrogen at 70-95 ℃ to obtain a polyurethane prepolymer, heating the polyurethane prepolymer and bisphenol A epoxy resin to 65-85 ℃ under the protection of nitrogen, and reacting for 1-3 hours to obtain the polyurethane epoxy resin.
It is a further object of the present invention to provide a molding composition prepared from the above-described polyurethane epoxy resin.
An environment-friendly high-strength impact-resistant molding compound comprises the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 10-35 parts of polyurethane epoxy resin, 30-60 parts of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 10-20 parts of epoxy curing agent, 1-3 parts of epoxy accelerator, and Al2O3100-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of short-cut reinforcing fiber and 50-100 parts of short-cut reinforcing fiber.
Preferably, the molding compound is prepared from the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 20-30 parts of polyurethane epoxy resin, 45-60 parts of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 12-18 parts of epoxy curing agent, 1.5-3 parts of epoxy accelerator, and Al2O3130-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of short-cut reinforcing fiber and 50-70 parts of short-cut reinforcing fiber.
Further preferably, the molding compound is prepared from the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 24-30 parts of polyurethane epoxy resin, 50-60 parts of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 15-18 parts of epoxy curing agent, 2-3 parts of epoxy accelerator, and Al2O3130-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of short-cut reinforcing fiber and 60-70 parts of short-cut reinforcing fiber.
The molding compound comprises the following raw materials:
the epoxy curing agent is an alkaline epoxy curing agent, specifically aliphatic diamine, polyamine, aromatic polyamine, dicyandiamide, imidazole and modified amine, preferably dicyandiamide, preferably micron-sized dicyandiamide, and further preferably dicyandiamide with the particle size of 5-30 μm.
The epoxy accelerator is imidazole, specifically 2-methylimidazole or 2-ethyl-4-methylimidazole, and more preferably 2-ethyl-4-methylimidazole.
The chopped reinforced fibers are 6-20mm glass fibers and 6-12mm carbon fibers.
The epoxy group-containing coupling agent is KH560 coupling agent.
The invention also provides a preparation method of the molding compound, which comprises the following steps: weighing epoxy resin, polyurethane epoxy resin and 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate according to the proportion, heating to 100-120 ℃, adding an epoxy curing agent into a kneading machine while stirring, stirring for 30-60 min, and then adding Al2O3And an epoxy group-containing coupling agent, fully and uniformly stirring, and then adding the reinforced chopped fibers, and stirring and combining for 5-10min to obtain the epoxy resin composition.
The molding compound provided by the invention has the following advantages:
1. the polyurethane epoxy resin provided by the invention comprises the following components:
the polyurethane itself is a large class of products, the functions are different, many of them are designed according to the performance requirements, in order to increase the rigidity, flexibility and flexibility of the epoxy resin, the inventor finds that the methylene structure can be introduced into the structure, and in order to select the proper raw materials, the inventor finds through a large number of experiments that: the product prepared by using the poly (ethylene adipate) glycol-diethylene glycol ester glycol is soft but low in strength, the reaction speed is too high when the diethylene glycol is used, the reaction is easy to lose control, and finally the preparation of the polyurethane epoxy resin by using the bisphenol A type epoxy resin, the poly (tetramethylene-co-ethyleneether) glycol, the 1, 3-propylene glycol and the diphenylmethane diisocyanate is determined.
Compared with CN104531034A (application No. CN201410529459.0, hereinafter referred to as 2014 patent), the polyurethane epoxy resin prepared by the present invention has the following differences:
the reaction principle is as follows: firstly, synthesizing a polyurethane prepolymer, and then reacting the polyurethane prepolymer with epoxy resin to form polyurethane epoxy resin;
on the raw materials: the 2014 patent uses raw materials of bisphenol A epoxy resin, polyester polyol, diphenylmethane diisocyanate, 1, 4-butanediol and dimethylolpropane.
The raw materials used in the present invention are bisphenol a type epoxy resin, poly (tetramethylene-co-ethyleneether) glycol, 1, 3-propanediol, and diphenylmethylene diisocyanate;
it is known that when preparing polyurethane epoxy resin, the longer the molecular chain segment in the raw material, the better the product flexibility, but not the longer, the longer the molecular chain of the raw material, which may cause some negative effects, such as good product flexibility but reduced strength, so the poly (tetramethylene-co-ethyleneether) glycol is selected.
The diphenylmethane diisocyanate has more methylene in structure than the diphenylmethane diisocyanate, and during reaction, the methylene exists in a prepolymer and even in a final polyurethane epoxy resin, so that the finally prepared product has better flexibility.
The 2014 patent does not mention which polyol the polyester polyol is, and the poly (tetramethylene-co-ethyleneether) glycol has more methylene groups than the conventional polyester polyol in structure, and the methylene groups can exist in prepolymer and even final polyurethane epoxy resin during reaction, so that the rigidity and toughness of the final prepared product are better.
On the product: the polyurethane epoxy structurally adds long methylene groups, combines the flexibility of poly (tetramethylene-co-ethyleneether) glycol with the rigidity and toughness of diphenylmethylene diisocyanate, and gives the polyurethane epoxy resin better impact toughness.
2. The molding compound provided by the invention comprises the following raw materials:
the used polyurethane epoxy resin is prepared by self, and a specific molecular chain structure endows the system with better impact toughness;
4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester is 3-functional epoxy resin containing 1 alicyclic epoxy group and 2 glycidyl ester groups in a molecular structure, has the dual characteristics of alicyclic epoxy and glycidyl ester, has better comprehensive performance, does not obviously increase brittleness due to the increase of functional groups and crosslinking density, and has better rigidity and toughness. The condensate has the characteristics of high temperature resistance, high strength, high adhesion and the like, and has good weather resistance, low temperature resistance and electrical insulation.
The used epoxy curing agent is an alkaline epoxy curing agent, preferably dicyandiamide, particularly 5-30 mu m dicyandiamide has the best effect in experiments, the compatibility of the 5-30 mu m dicyandiamide and epoxy resin is better, the curing reaction speed is higher, and the mechanical property of a cured product is higher;
the used epoxy accelerator can improve the curing efficiency, reduce the curing temperature and simultaneously take the storage period of the system into consideration;
the curing agent/accelerator system has latency, so that the storage stability of the molding compound is good, the using amount of the curing agent/accelerator system is within the range, if the using amount is too low, the curing of the system is insufficient, and the performance of the resin is reduced; too high, not only the properties of the molding materials but also the storage stability are affected.
The used epoxy group-containing coupling agent can improve the interface between the resin and the inorganic material;
the molding compound prepared from the raw materials has the advantages of good filling property, high fluidity, high curing speed and no VOC (volatile organic compound) emission. Meanwhile, the obtained molding compound has the advantages of high mechanical strength, high temperature resistance grade, high impact strength, low water absorption and the like after being cured and processed. Usually, the obtained molding compound is added into a mold with the temperature of 160-180 ℃, cured for 10-30 min, and cooled to room temperature to be molded.
3. Compared with the 2014 patent in the prior art, the molding compound provided by the invention has the following differences:
1) on the raw materials:
three resins were used in combination: the 2014 patent adopts a combination of polyurethane modified epoxy resin, phenolic resin and polysulfide rubber, and the invention adopts bisphenol A epoxy resin, polyurethane modified epoxy resin and 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, firstly, the polyurethane epoxy resin has better flexibility than the polyurethane epoxy resin provided in 2014, and compared with the polysulfide rubber, the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester has better rigidity, strength and heat resistance. Compared with the phenolic resin provided in 2014, the bisphenol A epoxy resin provided by the invention has better comprehensive performance.
2) Curing agent:
in the 2014 patent, dimethylamine propylamine, diethylamine propylamine and beta-hydroxyethyl ethylenediamine are adopted, dicyandiamide is used in the invention, and micron-sized dicyandiamide with the particle size of 5-30 mu m is preferred, firstly, dicyandiamide is solid at normal temperature, compared with the 2014 patent, the liquid amine is low in organic volatile matter and has better environmental protection performance, and secondly, compared with the 2014 patent, the micron-sized dicyandiamide for curing epoxy resin, the micron-sized dicyandiamide has higher strength and heat resistance.
3) Accelerator (b):
in 2014, a composite accelerator, namely a combination of dicyandiamide and imidazole is used, and 2-ethyl-4-methylimidazole is selected to be matched with a curing agent micron-sized dicyandiamide to endow the molding compound with low-temperature latency and high-temperature rapid curing and forming performance. Compared with the prior art, the molding compound provided by the invention has the advantages of good filling property, high fluidity, high curing speed and the like, and the cured product has the advantages of high mechanical strength, high temperature resistance level, high impact strength, low water absorption and the like.
4. The invention has the following beneficial effects:
1) according to the invention, the molding compound prepared by introducing alicyclic epoxy and synthetic polyurethane epoxy resin ensures excellent impact resistance, bending property, stress cracking resistance and heat resistance;
2) according to the invention, the molding compound is ensured to have good storage stability and high-temperature rapid curing molding performance by optimizing the micron dicyandiamide/modified imidazole and the curing/promoting system.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1: polyurethane epoxy resin and preparation thereof
1. Raw materials: 100g of bisphenol A epoxy resin, 25g of poly (tetramethylene-co-ethyleneether) glycol, 15g of diphenylmethylene diisocyanate and 3g of 1, 3-propanediol.
2. The preparation method comprises the following steps:
weighing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate according to the proportion, heating to 75 ℃, and reacting for 2.5 hours under the protection of nitrogen. Then adding 1, 3-propylene glycol, and continuing to react for 2 hours at 85 ℃ under the protection of nitrogen to obtain the polyurethane prepolymer. And adding the bisphenol A epoxy resin into the polyurethane prepolymer, heating to 70 ℃, and reacting for 3 hours under the protection of nitrogen to obtain the polyurethane epoxy resin.
Example 2: polyurethane epoxy resin and preparation thereof
1. Raw materials: 100g of bisphenol A epoxy resin, 30g of poly (tetramethylene-co-ethyleneether) glycol, 20g of diphenylmethylene diisocyanate and 2g of 1, 3-propanediol.
2. The preparation method comprises the following steps: weighing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate according to the proportion, heating to 80 ℃, and reacting for 2 hours under the protection of nitrogen. Then adding 1, 3-propylene glycol, and continuing to react for 2 hours at 85 ℃ under the protection of nitrogen to obtain the polyurethane prepolymer. And adding the bisphenol A epoxy resin into the polyurethane prepolymer, heating to 70 ℃, and reacting for 3 hours under the protection of nitrogen to obtain the polyurethane epoxy resin.
Example 3: polyurethane epoxy resin and preparation thereof
1. Raw materials: 100g of bisphenol A epoxy resin, 25g of poly (tetramethylene-co-ethyleneether) glycol, 10g of diphenylmethylene diisocyanate and 2g of 1, 3-propanediol.
2. The preparation method comprises the following steps: weighing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate according to the proportion, heating to 75 ℃, and reacting for 2 hours under the protection of nitrogen. Then adding 1, 3-propylene glycol, and continuing to react for 1 hour at the temperature of 90 ℃ under the protection of nitrogen to obtain the polyurethane prepolymer. And adding the bisphenol A epoxy resin into the polyurethane prepolymer, heating to 80 ℃, and reacting for 2 hours under the protection of nitrogen to obtain the polyurethane epoxy resin.
Example 4: polyurethane epoxy resin and preparation thereof
1. Raw materials: 100g of bisphenol A epoxy resin, 35g of poly (tetramethylene-co-ethyleneether) glycol, 12g of diphenylmethylene diisocyanate, and 3g of 1, 3-propanediol.
2. The preparation method comprises the following steps:
weighing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate according to the proportion, heating to 70 ℃, and reacting for 3 hours under the protection of nitrogen. Then adding 1, 3-propylene glycol, and continuing to react for 3 hours at the temperature of 80 ℃ under the protection of nitrogen to obtain the polyurethane prepolymer. And adding the bisphenol A epoxy resin into the polyurethane prepolymer, heating to 85 ℃, and reacting for 1.5 hours under the protection of nitrogen to obtain the polyurethane epoxy resin.
Experimental example 1: comparison of impact toughness
1. Grouping experiments: examples 1-4, comparative example 1, refer to the urethane epoxy resin prepared by the method of example 1 in the 2014 patent (CN104531034A, application No. CN 201410529459.0).
2. The experimental method comprises the following steps: putting the measured polyurethane epoxy resin into a beaker, heating to 80-100 ℃, adding the micron dicyandiamide and the 2-ethyl-4-methylimidazole, uniformly stirring, defoaming in vacuum, and pouring into a preheating mold. Curing at 160 ℃ for 1 h. The prepared test sample is tested according to GB/T1043.1-2008 plastic simple beam impact performance part 1: carrying out impact toughness test on the non-instrumented impact test scheme; GBT9341 Plastic bending property test method for bending strength test.
3. The experimental results are as follows: see Table 1
Table 1: properties of urethane epoxy resins obtained in examples 1 to 4 and comparative example
The results in Table 1 show that examples 1,2, 4 are superior in impact strength to comparative examples, examples 1,2 are superior in flexural strength to comparative examples, and examples 3, 4 are slightly superior in impact strength to comparative examples, although the flexural strength is comparable to comparative examples, so that examples 3 and 4 are superior in impact toughness. The best results are obtained in example 2 with respect to impact toughness.
The result shows that the polyurethane resin prepared by the invention has better impact toughness.
Example 5: environment-friendly high-strength impact-resistant molding compound
1. Raw materials:
100g of bisphenol A epoxy resin, 20g of polyurethane epoxy resin (prepared from example 1), 45g of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 12g of 5 μm dicyandiamide, 1.5g of 2-ethyl-4-methylimidazole, Al2O3150g, 0.25g of KH560 coupling agent and 60g of 12mm glass fiber.
2. The preparation method comprises the following steps:
weighing bisphenol A epoxy resin, polyurethane epoxy resin and 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to raw materials, mixing and heating to 110 ℃, fully stirring, adding curing agent and accelerator, stirring and reacting for 30min, adding Al2O3Mixing with KH560 coupling agent, stirring, adding glass fiber, and kneading for 8 min. The obtained molding compound is pressed and cured for 15min in a mold at 170 ℃.
Example 6: environment-friendly high-strength impact-resistant molding compound
1. Raw materials: 100g of bisphenol A epoxy resin, 30g of polyurethane epoxy resin (prepared from example 3), 50g of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 15g of 10 μm dicyandiamide, 2g of 2-ethyl-4-methylimidazole, Al2O3180g, 0.45g of KH560 coupling agent and 50g of 12mm carbon fiber.
2. The preparation method comprises the following steps:
weighing bisphenol A epoxy resin, polyurethane epoxy resin and 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to raw materials, mixing and heating to 100 ℃, fully stirring, adding curing agent and accelerator, stirring and reacting for 30min, adding Al2O3And KH560 coupling agent, adding carbon fiber, and kneading for 10 min. The obtained molding compound is pressed and cured for 5min in a mold at 180 ℃.
Example 7: environment-friendly high-strength impact-resistant molding compound
1. Raw materials: bisphenol A epoxy resin 100g25g of urethane epoxy resin (prepared in example 1), 60g of diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, 18g of 20 μm dicyandiamide, 2.5g of 2-ethyl-4-methylimidazole, and Al2O3200g of KH560 coupling agent, 0.5g of 20mm glass fiber, and 20g of 12mm carbon fiber.
2. The preparation method comprises the following steps:
weighing bisphenol A epoxy resin, polyurethane epoxy resin and 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to raw materials, mixing and heating to 100 ℃, fully stirring, adding curing agent and accelerator, stirring and reacting for 30min, adding Al2O3Mixing with KH560 coupling agent, stirring, adding glass fiber and carbon fiber, and kneading for 10 min. The obtained molding material is pressed and cured for 10min at 175 ℃ in a mold.
Example 8: environment-friendly high-strength impact-resistant molding compound
1. Raw materials: 100g of bisphenol A epoxy resin, 24g of polyurethane epoxy resin (prepared from example 2), 52g of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 15g of 30-micron dicyandiamide, 3g of imidazole curing agent and Al2O3130g of KH560 coupling agent, 0.2g of 12mm carbon fiber, and 20g of 6mm glass fiber.
2. The preparation method comprises the following steps:
weighing bisphenol A epoxy resin, polyurethane epoxy resin and 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to raw materials, mixing and heating to 110 ℃, fully stirring, adding curing agent and accelerator, stirring and reacting for 30min, adding Al2O3And KH560 coupling agent, adding carbon fiber and glass fiber, kneading for 10min, and pressing and curing the obtained molding compound in a mold at 165 deg.C for 15 min.
Comparative example 1: (conventional molding compound in which the polyurethane epoxy resin and the micron-sized dicyandiamide synthesized in the invention are not used)
Ordinary molding compound: weighing 100g of bisphenol A epoxy resin, mixing and heating to 100 ℃, fully stirring, adding 20g of common dicyandiamide while stirring, reacting for 30min while stirring, adding Al2O3120g of the mixture was sufficiently stirred, 80g of 12mm glass fiber was added thereto, and the mixture was kneadedFor 10 min. The obtained molding material is pressed and cured for 15min at 185 ℃ in a mold.
Comparative example 2: reference is made to the moulding compound obtained in example 1 of the patent application CN104531034A (application No. CN 201410529459.0).
Experimental examples 5-8 Performance tests:
1. experimental samples: the molding materials prepared in examples 5 to 8, the molding materials prepared in comparative examples 1 and 2.
2. The detection method comprises the following steps:
GBT1451-2005 (national Standard of the people's republic of China) fiber reinforced plastic SIMspecimen beam impact toughness;
GBT1449-2005 (national Standard of the people's republic of China) fiber reinforced plastic bending property test method;
the glass transition temperature is measured by a Differential Scanning Calorimeter (DSC) produced by the company of speed tolerance, the measurement temperature is 30-250 ℃, and the heating rate is 5 ℃/min.
3. The experimental results are as follows: see Table 2
Table 2: properties of the Molding materials obtained in examples 5 to 8 and comparative example
Table 2 the results show: examples 5-8 are superior to comparative example 1 in both impact toughness and bending performance, with examples 6-8 being more effective in impact toughness and bending performance, and even better than comparative examples 1 and 2.
The result shows that the molding compound provided by the invention is an environment-friendly molding compound with high strength and strong impact resistance.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and it should be understood by those skilled in the art that the specific embodiments of the present invention can be modified or substituted with equivalents with reference to the above embodiments, and any modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims to be appended.
Claims (7)
1. An environment-friendly high-strength impact-resistant molding compound comprises the following raw materials in parts by mass: 100 parts of bisphenol A epoxy resin, 10-35 parts of polyurethane epoxy resin, 30-60 parts of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 10-20 parts of epoxy curing agent, 1-3 parts of epoxy accelerator, and Al2O3100-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of epoxy group-containing coupling agent and 50-100 parts of chopped reinforced fiber, wherein the epoxy curing agent is dicyandiamide with the particle size of 5-30 mu m, the epoxy accelerator is 2-ethyl-4-methylimidazole, the epoxy group-containing coupling agent is KH560 coupling agent, and the chopped reinforced fiber is 6-20mm glass fiber and 6-12mm carbon fiber;
the polyurethane epoxy resin is prepared from the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 10-35 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-4 parts of 1, 3-propylene glycol and 10-20 parts of diphenyl methylene diisocyanate, and the preparation method comprises the following steps:
weighing epoxy resin, polyurethane epoxy resin and 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate according to the proportion, heating to 100-120 ℃, adding an epoxy curing agent into a kneading machine while stirring, stirring for 30-60 min, and then adding Al2O3And an epoxy group-containing coupling agent, fully and uniformly stirring, and then adding the reinforced chopped fibers, stirring and kneading for 5-10min to obtain the epoxy resin.
2. The molding compound of claim 1, wherein the molding compound is prepared from the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 20-30 parts of polyurethane epoxy resin, 45-60 parts of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 12-18 parts of epoxy curing agent, 1.5-3 parts of epoxy accelerator, and Al2O3130-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of short-cut reinforcing fiber and 50-70 parts of short-cut reinforcing fiber.
3. The molding compound of claim 1, wherein the molding compound is prepared from the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 24-30 parts of polyurethane epoxy resin, 4, 5-epoxy cyclohexane-50-60 parts of 1, 2-dicarboxylic acid diglycidyl ester, 15-18 parts of epoxy curing agent, 2-3 parts of epoxy accelerator and Al2O3130-200 parts of epoxy group-containing coupling agent, 0.2-0.5 part of short-cut reinforcing fiber and 60-70 parts of short-cut reinforcing fiber.
4. The molding compound of claim 1, wherein said urethane epoxy resin is prepared from the following ingredients in parts by weight: 100 parts of bisphenol A epoxy resin, 25-35 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-3 parts of 1, 3-propylene glycol and 10-20 parts of diphenylmethylene diisocyanate.
5. The molding compound of claim 1, wherein said urethane epoxy resin is prepared from the following ingredients in parts by weight: 100 parts of bisphenol A epoxy resin, 25-30 parts of poly (tetramethylene-co-ethyleneether) glycol, 2-3 parts of 1, 3-propylene glycol and 15-20 parts of diphenylmethylene diisocyanate.
6. A moulding compound according to claim 4 or 5, characterized in that the method for the preparation of the polyurethane epoxy resin comprises the following steps: pretreating raw materials for preparing the molding compound in the claim 4 or 5 to the water content of below 0.2wt%, mixing poly (tetramethylene-co-ethyleneether) glycol and diphenylmethylene diisocyanate, heating to 65-85 ℃, reacting for 1-4 hours under the protection of nitrogen, adding 1, 3-propylene glycol, continuing to react for 1-4 hours under the protection of nitrogen at 70-95 ℃ to obtain a polyurethane prepolymer, and then heating the polyurethane prepolymer and bisphenol A epoxy resin to 65-85 ℃ to react for 1-3 hours under the protection of nitrogen to obtain the polyurethane epoxy resin.
7. The preparation method of the molding compound is characterized by comprising the following steps: weighing the epoxy resin, the polyurethane epoxy resin and the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to the proportion of any one of claims 1 to 6, heating to 100-120 ℃, adding the epoxy curing agent into a kneader while stirring, stirring for 30-60 min, and then adding Al2O3And contain a ringAnd (3) fully and uniformly stirring the oxygen group coupling agent, and then adding the enhanced chopped fibers, stirring and kneading for 5-10min to obtain the epoxy resin modified epoxy resin.
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| CN104531034A (en) * | 2014-10-09 | 2015-04-22 | 广东新展化工新材料有限公司 | Polyurethane-modified epoxy resin adhesive and preparation method thereof |
| CN106397706A (en) * | 2015-07-30 | 2017-02-15 | 株洲时代新材料科技股份有限公司 | High-hardness epoxy modified polyurethane composite material and preparation method thereof |
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| DK2668221T3 (en) * | 2011-01-28 | 2016-01-25 | Covestro Deutschland Ag | Enhanced polyurethanpultrudater and preparation thereof |
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| US5783652A (en) * | 1997-11-04 | 1998-07-21 | Bayer Corporation | Reactivity improvement of urethane prepolymers of allophanate-modified diphenylmethane diisocyanates |
| CN101870798A (en) * | 2010-06-29 | 2010-10-27 | 北京玻钢院复合材料有限公司 | Epoxy resin dough moulding compound and preparation method thereof |
| CN103740059A (en) * | 2013-12-31 | 2014-04-23 | 苏州巨峰电气绝缘系统股份有限公司 | Low-temperature-resistant insulating impregnating resin and preparation method thereof |
| CN104531034A (en) * | 2014-10-09 | 2015-04-22 | 广东新展化工新材料有限公司 | Polyurethane-modified epoxy resin adhesive and preparation method thereof |
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