CN106009488B - A kind of preparation method of phenolic resin-base composite - Google Patents

A kind of preparation method of phenolic resin-base composite Download PDF

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Publication number
CN106009488B
CN106009488B CN201610531589.7A CN201610531589A CN106009488B CN 106009488 B CN106009488 B CN 106009488B CN 201610531589 A CN201610531589 A CN 201610531589A CN 106009488 B CN106009488 B CN 106009488B
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minutes
calcium sulfate
oyster shell
phenolic resin
shell whiting
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CN106009488A (en
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魏国祯
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JIANGSU JINLING SPECIAL PAINT CO Ltd
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Quanzhou Zhongyan Intelligent Electromechanical Resarch Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/58—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/58—Measuring, controlling or regulating
    • B29C2043/5808—Measuring, controlling or regulating pressure or compressing force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/58—Measuring, controlling or regulating
    • B29C2043/5816—Measuring, controlling or regulating temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of preparation method of phenolic resin-base composite, and its step is as follows：(1) dry, shell after drying is soaked in sodium hydroxide solution by shell after being dried after cooling, take out after shell is cleaned, dried after washing, oyster shell whiting is obtained after grinding；(2) oyster shell whiting is added in silane coupler solution and stirred, it is ultrasonically treated to obtain being modified oyster shell whiting；(3) calcium sulfate crystal whiskers are configured to after suspension slurry, stirring add odium stearate, continue to take out after stirring, filtration cakes torrefaction is obtained wastewaters with modified calcium sulfate whiskers by washing, filtering；(4) phenolic resin, modified oyster shell whiting, wastewaters with modified calcium sulfate whiskers are added into stirred tank stirring, drying to constant weight, cooling obtains compound；(5) compound is put into mould, mould is put into hot press, pressure release is deflated after precompressed, and then hot pressing, drying, cooling obtains composite.The composite that the present invention is prepared has preferable hardness and mechanical property.

Description

A kind of preparation method of phenolic resin-base composite
Technical field：
The present invention relates to a kind of construction material, more particularly to a kind of preparation method of phenolic resin-base composite.
Background technology：
Phenolic resin is commonly called as phenolic moulding powder, is invented in 1872, and input industrial production in 1909, is that history is most long-drawn-out in the world Long plastics and the one type of most important thermosetting plastics.Phenoplasts generally can be divided into non-laminated phenolics and The class of laminated phenolics two, non-laminated phenolics can be divided into Catalin and phenoplast molding compound again.Phenoplasts because With excellent heat resistance and preferable cost performance, still have the advantages that other general-purpose plastics are incomparable so far, use extensively Make electrically insulating material, furniture element, commodity, handicraft, construction material etc..
For example, Publication No. CN1123599C, publication date are 2003.10.08, apply for that artificial Chinese Academy of Sciences's chemistry is ground Study carefully Chinese patent disclose " a kind of preparation method of nano-class phenolic resin/day composition ", it enters as follows OK：1st, phenolic resin is melted at moderate temperatures and be in a liquid state；2nd, lower add relative to phenolic resin and phyllosilicate is stirred The clay of laminar silicate of the gross weight 1-20% parts by weight of clay；3rd, insulated and stirred is continued 10-200 minutes.The patent technique Process is simple and easy to apply, but the hardness and mechanical strength of its composite prepared (especially shock resistance) are not very It is good, limit its application and promote.
The content of the invention：
The technical problem to be solved in the present invention is to provide a kind of preparation method of phenolic resin-base composite, prepare Composite has preferable hardness and mechanical property.In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in sodium hydroxide solution afterwards, is taken out after 2 days, and vacuum baking is placed in after being washed with deionized Dried 2 hours at 80 DEG C in case, move into after being ground in grinder and obtain oyster shell whiting；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting；
(3) calcium sulfate crystal whiskers are added in absolute ethyl alcohol and is configured to suspension slurry, moved in water bath containers and stir 20 minutes After add odium stearate, continue to take out after stirring 30 minutes, be washed with deionized, filter, filter cake is placed at 110 DEG C and dried 4 hours, obtain wastewaters with modified calcium sulfate whiskers；
(4) wastewaters with modified calcium sulfate whiskers that the modification oyster shell whiting that obtains phenolic resin, step (2), step (3) are obtained is added Stirred tank is stirred 20 minutes, is moved in baking oven and is dried at 80 DEG C to constant weight, naturally cools to and compound is obtained after room temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, then hot pressing 1 hour, move in baking oven and dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin is obtained after room temperature Based composites.
Preferably, in step (1) of the present invention, the mass fraction of sodium hydroxide solution is 5%.
Preferably, in step (1) of the present invention, the time of grinding is 4 hours.
Preferably, in step (2) of the present invention, oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100.
Preferably, in step (3) of the present invention, the mass fraction of suspension slurry is 10%.
Preferably, in step (3) of the present invention, the temperature of water-bath is 80 DEG C.
Preferably, in step (3) of the present invention, calcium sulfate crystal whiskers, absolute ethyl alcohol, the weight ratio of odium stearate are 25: 100:2。
Preferably, in step (4) of the present invention, phenolic resin, modified oyster shell whiting, the weight ratio of modified calcium sulfate are 100:(2-5):(12-16)。
Preferably, in step (5) of the present invention, the temperature of precompressed is 140 DEG C, and pressure is 20MPa.
Preferably, in step (5) of the present invention, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa.
Compared with prior art, the invention has the advantages that：
1) oyster shell whiting is a kind of natural organic hybrid filler, and its main component is calcium carbonate, with good hardness and Intensity, by producing stronger interface cohesion between the modified oyster shell whiting energy in the surface of silane coupler and phenolic resin so that Oyster shell whiting can be uniformly distributed in phenolic resin as matrix resin and play preferable humidification, effectively increase the hard of composite Degree, tensile strength, bending strength.
2) calcium sulfate crystal whiskers are the fibrous materials grown with single crystal form of calcium sulfate, the atom row with high-sequential Row, therefore possess very high intensity and modulus, it can be good at being scattered in resin matrix simultaneously by odium stearate is modified Combined closely with phenolic resin, so as to play good humidification to phenolic resin, effectively increase the hardness of composite And intensity；When stress is in composite, because intensity, the modulus of calcium sulfate crystal whiskers are above phenolic resin, so sulphur Sour calcium pyroborate can locally resist stress, effect of the reduction stress to phenolic resin, and calcium sulfate crystal whiskers can trigger micro-crack, The extension of crackle is prevented, is conducive to stress to transmit, so as to effectively improve the toughness of composite.
Embodiment：
Describe the present invention in detail below in conjunction with specific embodiment, herein illustrative examples and explanation of the invention For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, takes out, be washed with deionized water after 2 days afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:4:Modification oyster shell whiting that 13 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers adds stirred tank and stirred 20 minutes, moves in baking oven and is dried at 80 DEG C to constant weight, naturally cools to room temperature After obtain compound；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
Embodiment 2
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, takes out, be washed with deionized water after 2 days afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:3:Modification oyster shell whiting that 12 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers add stirred tank stir 20 minutes, move in baking oven and dried at 80 DEG C to constant weight, naturally cool to room Compound is obtained after temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
Embodiment 3
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, is taken out after 2 days, use deionized water afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:5:Modification oyster shell whiting that 12.5 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers add stirred tank stir 20 minutes, move in baking oven and dried at 80 DEG C to constant weight, naturally cool to room Compound is obtained after temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
Embodiment 4
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, is taken out after 2 days, use deionized water afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:2:Modification oyster shell whiting that 16 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers adds stirred tank and stirred 20 minutes, moves in baking oven and is dried at 80 DEG C to constant weight, naturally cools to room temperature After obtain compound；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to after room temperature and obtain a kind of phenolic resin base composite wood Material.
Embodiment 5
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, takes out, be washed with deionized water after 2 days afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:2.5:Modification oyster shell whiting that 14 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers add stirred tank stir 20 minutes, move in baking oven and dried at 80 DEG C to constant weight, naturally cool to room Compound is obtained after temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
Embodiment 6
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, is taken out after 2 days, use deionized water afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:4.5:Modification oyster shell whiting that 15 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers add stirred tank stir 20 minutes, move in baking oven and dried at 80 DEG C to constant weight, naturally cool to room Compound is obtained after temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
Embodiment 7
A kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to and drying obtained after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, takes out, be washed with deionized water after 2 days afterwards It is placed in vacuum drying oven at 80 DEG C and dries 2 hours after washing, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained is added Stirred 10 minutes in silane coupler solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, Oyster shell whiting, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, temperature is moved to To add odium stearate after being stirred 20 minutes in 80 DEG C of water bath containers, continue to take out after stirring 30 minutes, be washed with deionized water Wash, filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, calcium sulfate crystal whiskers, anhydrous second Alcohol, the weight ratio of odium stearate are 25:100:2；
(4) it is 100 by weight ratio:3.5:Modification oyster shell whiting that 14.5 phenolic resin, step (2) are obtained, step (3) The wastewaters with modified calcium sulfate whiskers arrived adds stirred tank and stirred 20 minutes, moves in baking oven and is dried at 80 DEG C to constant weight, is naturally cooled to Compound is obtained after room temperature；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, pressure release after precompressed 2 minutes Deflate, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, moves in baking oven and is dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
After tested, the hardness of composite and comparative example, tensile strength, bending strength, impact made from embodiment 1-7 Intensity, wherein, comparative example is Publication No. CN1123599C Chinese patent；
Hardness is tested using plastics ball indentation hardness analyzer, and the diameter D of baton round is 6mm, and pressure p is 372N, is continued Time is 30s, and hardness H (N/cm2) calculation formula is：H=21p/【25πD(h-0.04)】, h (mm) is sample depth of cup；
Tensile strength is tested by GB/T1447-2005, and bending strength is tested by GB/T1449-2005, impact Intensity is tested by GB/T1451-2005：
Hardness, tensile strength, bending strength, the impact strength of composite produced by the present invention are better than comparative example.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause This, those of ordinary skill in the art is without departing from disclosed spirit and institute under technological thought such as All equivalent modifications completed or change, should be covered by the claim of the present invention.

Claims (1)

1. a kind of preparation method of phenolic resin-base composite, its step is as follows：
(1) by shell be washed with deionized water only, remove surface horny layer after dry, naturally cool to shellfish after being dried after room temperature Shell, shell after drying is soaked in the sodium hydroxide solution that mass fraction is 5%, taken out after 2 days, after being washed with deionized It is placed in vacuum drying oven at 80 DEG C and dries 2 hours, moves into grinding in grinder and obtain oyster shell whiting after 4 hours；
(2) silane coupler is dissolved in acetone and obtains silane coupler solution, the oyster shell whiting that step (1) is obtained adds silane Stirred 10 minutes in coupling agent solution, move into ultrasonic container ultrasonically treated 40 minutes, obtain being modified oyster shell whiting, wherein, shell Powder, silane coupler, the weight ratio of acetone are 15:1:100；
(3) calcium sulfate crystal whiskers are added to the suspension slurry for being configured to that mass fraction is 10% in absolute ethyl alcohol, it is 80 to move to temperature DEG C water bath containers in stirring add odium stearate after 20 minutes, continue to take out after stirring 30 minutes, be washed with deionized, mistake Filter, filter cake is placed at 110 DEG C and dried 4 hours, wastewaters with modified calcium sulfate whiskers is obtained, wherein, it is calcium sulfate crystal whiskers, absolute ethyl alcohol, hard The weight ratio of resin acid sodium is 25:100:2；
(4) it is 100 by weight ratio:3.5:Modification oyster shell whiting that 14.5 phenolic resin, step (2) are obtained, step (3) are obtained Wastewaters with modified calcium sulfate whiskers adds stirred tank and stirred 20 minutes, moves in baking oven and is dried at 80 DEG C to constant weight, naturally cools to room temperature After obtain compound；
(5) compound for obtaining step (4) is put into mould, and mould is put into hot press, and pressure release is put after precompressed 2 minutes Gas, the temperature of precompressed is 140 DEG C, and pressure is 20MPa, then hot pressing 1 hour, and the temperature of hot pressing is 150 DEG C, and pressure is 21MPa, Move in baking oven and dried 3.5 hours at 190 DEG C, naturally cool to and phenolic resin-base composite is obtained after room temperature.
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