CN105038118B - Urea resin matrix composite material and preparation method thereof - Google Patents
Urea resin matrix composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 29
- 239000011159 matrix material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000004645 aluminates Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 239000001023 inorganic pigment Substances 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000001404 mediated effect Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims 1
- -1 hexa-methylene four Amine Chemical compound 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 10
- 229920000069 polyphenylene sulfide Polymers 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Abstract
The present invention provides urea resin matrix composite material, and its component and parts by weight are：40~60 parts of Lauxite, 6~8 parts of PPS, 3~4 parts of compatilizer, 8~10 parts of hollow aluminum oxide microspheres, 2~5 parts of toughener, 15~20 parts of filler, 1~2 part of coupling agent, 1~2 part of curing agent, 0.5~1 part of pigment, 1~2 part of lubricant, 3~5 parts of stabilizer.Present invention also offers the preparation method of the composite.Skis urea resin matrix composite material provided by the invention has good toughness, hydrolytic resistance and heat resistance, can be applied to a variety of occasions.
Description
Technical field：
The present invention relates to a kind of composite, more particularly to urea resin matrix composite material and preparation method thereof.
Background technology：
Lauxite is also known as urea formaldehyde resin, english abbreviation UF, is that urea with formaldehyde in catalyst, (urge by alkalescence or acidity
Agent) under effect, Lauxite at initial stage is polycondensed into, then again under curing agent or promoter effect, forms insoluble, insoluble latter stage
Thermosetting resin.Lauxite color after solidification is more shallow than phenolic resin, and be translucent shape, weak acid resistant, weak base, insulating properties
Good, wearability is splendid, cheap.Nineteen twenty-four, developed by Qing An companies of Britain, nineteen twenty-eight begins to sell product, the mid-1930s
Yield reaches kiloton, and the eighties, world's annual production was more than 1.5Mt.Lauxite is daily mainly for the manufacture of moulded plastic, manufacture
Life product and electric parts, it can also make slurry, thick china, decorative panel for building of sheet material adhesive, paper and fabric etc., also can be used for
Water resistance and the less demanding product of dielectric properties, such as wiring board, switch, machine handle, meter case, knob, commodity, dress
Ornaments, mah-jong pieces, chamber pot lid, and the manufacture of part tableware.
Publication No. CN102731962A, publication date 2012.10.17, the artificial Nanjing College of Chemical Technology of application
Chinese patent application disclose " a kind of preparation method of urea resin matrix composite material ", its component includes urea, formaldehyde, solid
Agent, emulsifying agent, releasing agent, pigment, filler etc.；Preparation method is：Urea, formaldehyde and auxiliary material are first polymerized to Lauxite in advance,
The auxiliary agents such as Lauxite, curing agent, releasing agent are added into combination drying reactor, are well mixed, mixed through vacuum, polymerize it is obtained
Urea resin matrix composite material.4% or so, automaticity has larger carry for the control that the product moisture of the invention can be stablized
Height, operating environment have greatly improved.But, also there is the defects of certain in composite made from this method：Fragility is larger, no
Hydrolysis, heat resistance is also bad, and these defects constrain its application.
The content of the invention：
The technical problem to be solved in the present invention is to provide urea resin matrix composite material, it has good toughness, water-fast
Solution property and heat resistance, can be applied to a variety of occasions.
In order to solve the above technical problems, the technical scheme is that：
Urea resin matrix composite material, its component and parts by weight are：40~60 parts of Lauxite, 6~8 parts of PPS,
3~4 parts of compatilizer, 8~10 parts of hollow aluminum oxide microspheres, 2~5 parts of toughener, 15~20 parts of filler, 1~2 part of coupling agent, Gu
1~2 part of agent, 0.5~1 part of pigment, 1~2 part of lubricant, 3~5 parts of stabilizer.
Preferably, compatilizer of the present invention is EVA-g-MAH.
Preferably, toughener of the present invention is lignin.
Preferably, filler of the present invention is talcum powder or calcium carbonate.
Preferably, coupling agent of the present invention is aluminate coupling agent.
Preferably, curing agent of the present invention is citric acid.
Preferably, pigment of the present invention is inorganic pigment.
Preferably, lubricant of the present invention is calcium stearate.
Preferably, stabilizer of the present invention is hexa.
Another technical problem to be solved by the present invention is that provide the preparation method of above-mentioned urea resin matrix composite material.
In order to solve the above technical problems, technical scheme is：
The preparation method of urea resin matrix composite material, its step are as follows：
(1) hollow aluminum oxide microspheres are dissolved in magnetic agitation 2 hours in dry toluene, continued after adding aluminate coupling agent
Magnetic agitation 20 hours, cleaned 20 minutes with ethanol after taking-up, be placed in vacuum desiccator at 100 DEG C and dry 3 hours, after grinding
Modified aluminas tiny balloon is made；
(2) Lauxite, PPS, compatilizer are added into stirrer for mixing 10 minutes together, moved in double screw extruder
160-200 DEG C of temperature, rotating speed are melting extrusion under 800rpm, and blend composition is made；
(3) it is modified aluminas obtained by toughener, filler, curing agent, pigment, lubricant, stabilizer, step (1) is hollow
Microballoon, step (2) gained blend composition are put at being mediated 40 minutes, 70 DEG C in kneader and moudling powder are made after drying, crushing；
(4) moudling powder obtained by step (3) is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, forming temperature
For 145 DEG C, briquetting pressure 5Mpa, hardening time is 3 minutes, obtains urea resin matrix composite material.
Therefore compared with prior art, the invention has the advantages that：
(1) aluminum oxide has high intensity, high rigidity, resistant to elevated temperatures characteristic, and its tiny balloon has hollow structure, therefore also
With good heat-proof quality, but hollow aluminum oxide microspheres surface is in oleophobic property, and effective knot is hardly formed with Lauxite
Close, therefore the present invention carries out surface modification by aluminate coupling agent, aluminate coupling agent has both sexes structure, one part base
Group with hollow aluminum oxide microspheres surface occur bonding reaction, another part group have it is organophilic, with Lauxite matrix
It can organically combine so that hollow aluminum oxide microspheres can form effective interface cohesion with Lauxite, compound so as to greatly improve
The heat resistance of material；Hollow aluminum oxide microspheres are a kind of inorganic rigid materials, can be used as physical crosslinking point in the composite,
When composite is by external impacts, hollow aluminum oxide microspheres can play a part of stress concentration point, consume impact energy significantly,
Effectively increase the impact resistance and toughness of composite.
(2) polyphenylene sulfide is the crystalline thermoplastic engineering plastics containing thiophenyl on molecular backbone, is had resistance to well
High-temperature behavior and anti-hydrolytic performance, phenyl ring is introduced inside it after being blended with Lauxite, encloses the water suction of Lauxite
Group, therefore the hydrolytic resistance of composite is substantially increased, while further improves heat resistance.
Embodiment：
The present invention is described 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
Urea resin matrix composite material, its component and parts by weight are：45 parts of Lauxite, 6.5 parts of PPS, EVA-g-
3.8 parts of MAH, 8 parts of hollow aluminum oxide microspheres, 2.5 parts of lignin, 16 parts of talcum powder, 1.4 parts of aluminate coupling agent, citric acid 2
Part, 0.7 part of inorganic pigment, 1.8 parts of calcium stearate, 3.5 parts of hexa.
The step of its preparation method, is as follows：
(1) hollow aluminum oxide microspheres are dissolved in magnetic agitation 2 hours in dry toluene, continued after adding aluminate coupling agent
Magnetic agitation 20 hours, cleaned 20 minutes with ethanol after taking-up, be placed in vacuum desiccator at 100 DEG C and dry 3 hours, after grinding
Modified aluminas tiny balloon is made；
(2) Lauxite, PPS, compatilizer are added into stirrer for mixing 10 minutes together, moved in double screw extruder
160-200 DEG C of temperature, rotating speed are melting extrusion under 800rpm, and blend composition is made；
(3) it is modified aluminas obtained by toughener, filler, curing agent, pigment, lubricant, stabilizer, step (1) is hollow
Microballoon, step (2) gained blend composition are put at being mediated 40 minutes, 70 DEG C in kneader and moudling powder are made after drying, crushing；
(4) moudling powder obtained by step (3) is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, forming temperature
For 145 DEG C, briquetting pressure 5Mpa, hardening time is 3 minutes, obtains urea resin matrix composite material.
Embodiment 2
Urea resin matrix composite material, its component and parts by weight are：50 parts of Lauxite, 7.5 parts of PPS, EVA-g-
3.2 parts of MAH, 9.5 parts of hollow aluminum oxide microspheres, 3 parts of lignin, 15 parts of calcium carbonate, 1.2 parts of aluminate coupling agent, citric acid
1.4 parts, 0.9 part of inorganic pigment, 1.2 parts of calcium stearate, 4.5 parts of hexa.
Its preparation method is in the same manner as in Example 1.
Embodiment 3
Urea resin matrix composite material, its component and parts by weight are：40 parts of Lauxite, 7 parts of PPS, EVA-g-
3.5 parts of MAH, 8.5 parts of hollow aluminum oxide microspheres, 2 parts of lignin, 18 parts of calcium carbonate, 1.8 parts of aluminate coupling agent, citric acid
1.6 part, 0.2 part of inorganic pigment, 1 part of calcium stearate, 4 parts of hexa.
Its preparation method is in the same manner as in Example 1.
Embodiment 4
Urea resin matrix composite material, its component and parts by weight are：55 parts of Lauxite, 6 parts of PPS, EVA-g-
4 parts of MAH, 10 parts of hollow aluminum oxide microspheres, 4 parts of lignin, 20 parts of talcum powder, 1 part of aluminate coupling agent, 1.5 parts of citric acid,
0.6 part of inorganic pigment, 1.4 parts of calcium stearate, 5 parts of hexa.
Its preparation method is in the same manner as in Example 1.
Embodiment 5
Urea resin matrix composite material, its component and parts by weight are：60 parts of Lauxite, 6.6 parts of PPS, EVA-g-
3 parts of MAH, 8.8 parts of hollow aluminum oxide microspheres, 4.4 parts of lignin, 17 parts of calcium carbonate, 1.5 parts of aluminate coupling agent, citric acid 1
Part, 0.8 part of inorganic pigment, 1.6 parts of calcium stearate, 3 parts of hexa.
Its preparation method is in the same manner as in Example 1.
Embodiment 6
Urea resin matrix composite material, its component and parts by weight are：48 parts of Lauxite, 8 parts of PPS, EVA-g-
3.4 parts of MAH, 9.6 parts of hollow aluminum oxide microspheres, 5 parts of lignin, 19 parts of talcum powder, 2 parts of aluminate coupling agent, citric acid 1.2
Part, 0.5 part of inorganic pigment, 2 parts of calcium stearate, 3.3 parts of hexa.
Its preparation method is in the same manner as in Example 1.
After tested, the toughness of embodiment 1-6 and comparative example, hydrolytic resistance and heat resistance are as shown in the table, wherein,
Comparative example is Publication No. CN102731962A Chinese patent,
Toughness is tested the impact strength of determinand by GB/T 1043-1993；
Hydrolytic resistance test process is：Determinand is placed in boiling water after boiling 10 hours, it is tested after being cooled to room temperature
Mechanical property conservation rate；
Heat resistance is tested the heat distortion temperature of determinand by ASTM D648.
As seen from the above table, impact strength of the invention, stretching strength retentivity, bending strength conservation rate, heat distortion temperature
It is significantly better than comparative example, there is good toughness, hydrolytic resistance and heat resistance.
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 complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (8)
1. urea resin matrix composite material, it is characterised in that its component and parts by weight are：40~60 parts of Lauxite, PPS
6~8 parts, 3~4 parts of compatilizer, 8~10 parts of hollow aluminum oxide microspheres, 2~5 parts of toughener, 15~20 parts of filler, coupling agent 1~
2 parts, 1~2 part of curing agent, 0.5~1 part of pigment, 1~2 part of lubricant, 3~5 parts of stabilizer；The compatilizer is EVA-g-
MAH；The coupling agent is aluminate coupling agent.
2. urea resin matrix composite material according to claim 1, it is characterised in that：The toughener is lignin.
3. urea resin matrix composite material according to claim 1, it is characterised in that：The filler is talcum powder or carbonic acid
Calcium.
4. urea resin matrix composite material according to claim 1, it is characterised in that：The curing agent is citric acid.
5. urea resin matrix composite material according to claim 1, it is characterised in that：The pigment is inorganic pigment.
6. urea resin matrix composite material according to claim 1, it is characterised in that：The lubricant is calcium stearate.
7. urea resin matrix composite material according to claim 1, it is characterised in that：The stabilizer is hexa-methylene four
Amine.
8. the preparation method of the urea resin matrix composite material according to claim 1~7 any one, it is characterised in that：
Its step is as follows：
(1) hollow aluminum oxide microspheres are dissolved in magnetic agitation 2 hours in dry toluene, continue magnetic force after adding aluminate coupling agent
Stirring 20 hours, is cleaned 40 minutes after taking-up with ethanol, is placed in vacuum desiccator at 100 DEG C and is dried 3 hours, is made after grinding
Modified aluminas tiny balloon；
(2) Lauxite, PPS, compatilizer are added into stirrer for mixing 10 minutes together, moves to temperature in double screw extruder
160-200 DEG C, rotating speed be 800rpm under melting extrusion, be made blend composition；
(3) by toughener, filler, curing agent, pigment, lubricant, stabilizer, modified aluminas tiny balloon obtained by step (1),
Blend composition obtained by step (2) is put into is mediated 40 minutes, 70 DEG C in kneader at drying, crush after obtained moudling powder；
(4) moudling powder obtained by step (3) is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, and forming temperature is
145 DEG C, briquetting pressure 5Mpa, hardening time is 3 minutes, obtains urea resin matrix composite material.
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| CN105419704B (en) * | 2015-11-23 | 2018-07-31 | 苏州盖德精细材料有限公司 | A kind of urea-formaldehyde resin adhesive and preparation method thereof |
| CN109749355A (en) * | 2017-11-01 | 2019-05-14 | 丹阳市景顺塑料制品有限公司 | A kind of high-pressure plastic pipe |
| CN112143246A (en) * | 2020-09-19 | 2020-12-29 | 周静 | Application method of lignin in phenolic resin molding compound |
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| CN101654775A (en) * | 2008-08-21 | 2010-02-24 | 比亚迪股份有限公司 | Chemical plating material and preparation method thereof |
| CN103589281A (en) * | 2013-11-04 | 2014-02-19 | 上海电力学院 | High temperature resistant anticorrosion coating based on graphene and preparation method thereof |
| CN103642064A (en) * | 2013-11-29 | 2014-03-19 | 江门市奇德工程塑料科技有限公司 | Regeneration technique of urea-formaldehyde resin and composite material containing regenerated urea-formaldehyde resin |
| CN104098869A (en) * | 2014-08-04 | 2014-10-15 | 许立新 | Manufacturing method of high-intensity, lightweight and fireproof decorative material |
| CN104629147A (en) * | 2015-02-09 | 2015-05-20 | 杭州波达塑料科技股份有限公司 | High-temperature-resistant dewaxing molecular sieve double-wall corrugated pipe and preparation method |
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|---|---|---|---|---|
| CN101654775A (en) * | 2008-08-21 | 2010-02-24 | 比亚迪股份有限公司 | Chemical plating material and preparation method thereof |
| CN103589281A (en) * | 2013-11-04 | 2014-02-19 | 上海电力学院 | High temperature resistant anticorrosion coating based on graphene and preparation method thereof |
| CN103642064A (en) * | 2013-11-29 | 2014-03-19 | 江门市奇德工程塑料科技有限公司 | Regeneration technique of urea-formaldehyde resin and composite material containing regenerated urea-formaldehyde resin |
| CN104098869A (en) * | 2014-08-04 | 2014-10-15 | 许立新 | Manufacturing method of high-intensity, lightweight and fireproof decorative material |
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