CN105038118A - Urea-formaldehyde resin-based composite material and preparation method thereof - Google Patents
Urea-formaldehyde resin-based composite material and preparation method thereof Download PDFInfo
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- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 55
- 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 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title abstract description 8
- 239000000805 composite resin Substances 0.000 title abstract 4
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000007822 coupling agent Substances 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
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims description 34
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 150000004645 aluminates Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 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
- 239000000945 filler Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 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
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 230000001404 mediated effect Effects 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 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
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying 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
- 238000009413 insulation Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000002002 slurry 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 invention provides a urea-formaldehyde resin-based composite material. The urea-formaldehyde resin-based composite material comprises, by weight, 40 to 60 parts of urea-formaldehyde resin, 6 to 8 parts of PPS, 3 to 4 parts of a compatilizer, 8 to 10 parts of alumina hollow microsphere, 2 to 5 parts of a flexibilizer, 15 to 20 parts of a filling material, 1 to 2 parts of a coupling agent, 1 to 2 parts of a curing agent, 0.5 to 1 part of pigment, 1 to 2 parts of a lubricant and 3 to 5 parts of a stabilizing agent. The invention also provides a preparation method for the composite material. The urea-formaldehyde resin-based composite material for skis has good toughness, hydrolysis resistance and heat resistance and can be applied to a plurality of occasions.
Description
Technical field:
The present invention relates to a kind of matrix material, particularly relate to urea resin matrix composite material and preparation method thereof.
Background technology:
Urea-formaldehyde resin is also known as urea-formaldehyde resin, english abbreviation is UF, be urea and formaldehyde under catalyzer (alkalescence or an acidic catalyst) acts on, polycondensation becomes initial stage urea-formaldehyde resin, and then under solidifying agent or promoter effect, form insoluble, not molten thermosetting resin in latter stage.Urea-formaldehyde resin color after solidification is more shallow than resol, and be translucent shape, weak acid resistant, weak base, good insulation preformance, and wear resistance is splendid, low price.Nineteen twenty-four, by Qing An company of Britain develop, nineteen twenty-eight begin sell product, the mid-1930s output reach kiloton, the eighties, world's annual production was more than 1.5Mt.Urea-formaldehyde resin is mainly for the manufacture of moulded plastics, manufacture daily life product and electric parts, also can make the slurry, thick china, decorative panel for building etc. of sheet material tackiness agent, paper and fabric, also can be used for water tolerance and the less demanding goods of dielectric properties, as wiring board, switch, machine handle, meter case, knob, daily necessities, ornament, mah-jong pieces, chamber pot lid, and the manufacture of part tableware.
The Chinese patent application that publication number is CN102731962A, publication date is 2012.10.17, application people is Nanjing College of Chemical Technology discloses " a kind of preparation method of urea resin matrix composite material ", and its component comprises urea, formaldehyde, solidifying agent, emulsifying agent, releasing agent, pigment, filler etc.; Preparation method is: urea, formaldehyde and auxiliary material are first polymerized to urea-formaldehyde resin in advance, the auxiliary agents such as urea-formaldehyde resin, solidifying agent, releasing agent are added combination drying reactor, mixes, through vacuum mixing, the obtained urea resin matrix composite material of polymerization.The product moisture of this invention can be stable control about 4%, level of automation improves a lot, and operating environment has greatly improved.But, also there is certain defect in the matrix material that the method obtains: fragility is comparatively large, and not hydrolysis, thermotolerance is not good yet, and these defects constrain its range of application.
Summary of the invention:
The technical problem to be solved in the present invention is to provide urea resin matrix composite material, and it has good toughness, hydrolytic resistance and thermotolerance, can be applicable to multiple occasion.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 40 ~ 60 parts, PPS6 ~ 8 part, compatilizer 3 ~ 4 parts, hollow aluminum oxide microspheres 8 ~ 10 parts, toughner 2 ~ 5 parts, filler 15 ~ 20 parts, coupling agent 1 ~ 2 part, 1 ~ 2 part, solidifying agent, pigment 0.5 ~ 1 part, lubricant 1 ~ 2 part, stablizer 3 ~ 5 parts.
Preferably, compatilizer of the present invention is EVA-g-MAH.
Preferably, toughner of the present invention is xylogen.
Preferably, filler of the present invention is talcum powder or calcium carbonate.
Preferably, coupling agent of the present invention is aluminate coupling agent.
Preferably, solidifying agent of the present invention is citric acid.
Preferably, pigment of the present invention is mineral dye.
Preferably, lubricant of the present invention is calcium stearate.
Preferably, stablizer of the present invention is vulkacit H.
Another technical problem that the present invention will solve is to provide the preparation method of above-mentioned urea resin matrix composite material.
For solving the problems of the technologies described above, technical scheme is:
The preparation method of urea resin matrix composite material, its step is as follows:
(1) hollow aluminum oxide microspheres to be dissolved in dry toluene magnetic agitation 2 hours, magnetic agitation is continued 20 hours after adding aluminate coupling agent, with ethanol purge 20 minutes after taking out, to be placed at vacuum drier 100 DEG C dry 3 hours, obtained modified aluminas tiny balloon after grinding;
(2) urea-formaldehyde resin, PPS, compatilizer are added stirrer for mixing 10 minutes together, to move in twin screw extruder temperature 160-200 DEG C, rotating speed is melt extrude under 800rpm, obtained blend composition;
(3) toughner, filler, solidifying agent, pigment, lubricant, stablizer, step (1) gained modified aluminas tiny balloon, step (2) gained blend composition put into kneader and mediated 40 minutes, dry at 70 DEG C, pulverize rear obtained molding powder;
(4) step (3) gained molding powder is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, and mold temperature is 145 DEG C, and forming pressure is 5Mpa, and set time is 3 minutes, obtains urea resin matrix composite material.
Therefore compared with prior art, the present invention has following beneficial effect:
(1) aluminum oxide has high strength, high rigidity, resistant to elevated temperatures characteristic, its tiny balloon has hollow structure, therefore also there is good heat-proof quality, but hollow aluminum oxide microspheres surface is in oleophobic property, be difficult to be formed effectively combine with urea-formaldehyde resin, therefore the present invention carries out surface modification by aluminate coupling agent, aluminate coupling agent has both sexes structure, there is bonding reaction in one moieties and hollow aluminum oxide microspheres surface, another part group has close Organic Compound, can organically combine with urea-formaldehyde resin matrix, make hollow aluminum oxide microspheres and urea-formaldehyde resin can form effective interface cohesion, thus greatly improve the thermotolerance of matrix material, hollow aluminum oxide microspheres is a kind of inorganic rigid material, can be used as physical crosslinking point in the composite, when matrix material is subject to external impacts, hollow aluminum oxide microspheres can play the effect of focal point of stress, greatly consume impact energy, effectively improve impact resistance and the toughness of matrix material.
(2) polyphenylene sulfide is the crystalline thermoplastic engineering plastics containing thiophenyl on molecular backbone chain, there is good resistance to elevated temperatures and anti-hydrolytic performance, phenyl ring is introduced therein after blended with urea-formaldehyde resin, enclose the water suction group of urea-formaldehyde resin, therefore substantially increase the hydrolytic resistance of matrix material, further improves thermotolerance simultaneously.
Embodiment:
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 45 parts, PPS6.5 part, EVA-g-MAH3.8 part, hollow aluminum oxide microspheres 8 parts, 2.5 parts, xylogen, talcum powder 16 parts, aluminate coupling agent 1.4 parts, citric acid 2 parts, mineral dye 0.7 part, calcium stearate 1.8 parts, vulkacit H 3.5 parts.
The step of its preparation method is as follows:
(1) hollow aluminum oxide microspheres to be dissolved in dry toluene magnetic agitation 2 hours, magnetic agitation is continued 20 hours after adding aluminate coupling agent, with ethanol purge 20 minutes after taking out, to be placed at vacuum drier 100 DEG C dry 3 hours, obtained modified aluminas tiny balloon after grinding;
(2) urea-formaldehyde resin, PPS, compatilizer are added stirrer for mixing 10 minutes together, to move in twin screw extruder temperature 160-200 DEG C, rotating speed is melt extrude under 800rpm, obtained blend composition;
(3) toughner, filler, solidifying agent, pigment, lubricant, stablizer, step (1) gained modified aluminas tiny balloon, step (2) gained blend composition put into kneader and mediated 40 minutes, dry at 70 DEG C, pulverize rear obtained molding powder;
(4) step (3) gained molding powder is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, and mold temperature is 145 DEG C, and forming pressure is 5Mpa, and set time is 3 minutes, obtains urea resin matrix composite material.
Embodiment 2
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 50 parts, PPS7.5 part, EVA-g-MAH3.2 part, hollow aluminum oxide microspheres 9.5 parts, 3 parts, xylogen, 15 parts, calcium carbonate, aluminate coupling agent 1.2 parts, citric acid 1.4 parts, mineral dye 0.9 part, calcium stearate 1.2 parts, vulkacit H 4.5 parts.
Its preparation method in the same manner as in Example 1.
Embodiment 3
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 40 parts, PPS7 part, EVA-g-MAH3.5 part, hollow aluminum oxide microspheres 8.5 parts, 2 parts, xylogen, 18 parts, calcium carbonate, aluminate coupling agent 1.8 parts, citric acid 1.6 parts, mineral dye 0.2 part, calcium stearate 1 part, vulkacit H 4 parts.
Its preparation method in the same manner as in Example 1.
Embodiment 4
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 55 parts, PPS6 part, EVA-g-MAH4 part, hollow aluminum oxide microspheres 10 parts, 4 parts, xylogen, talcum powder 20 parts, aluminate coupling agent 1 part, citric acid 1.5 parts, mineral dye 0.6 part, calcium stearate 1.4 parts, vulkacit H 5 parts.
Its preparation method in the same manner as in Example 1.
Embodiment 5
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 60 parts, PPS6.6 part, EVA-g-MAH3 part, hollow aluminum oxide microspheres 8.8 parts, 4.4 parts, xylogen, 17 parts, calcium carbonate, aluminate coupling agent 1.5 parts, citric acid 1 part, mineral dye 0.8 part, calcium stearate 1.6 parts, vulkacit H 3 parts.
Its preparation method in the same manner as in Example 1.
Embodiment 6
Urea resin matrix composite material, its component and parts by weight are: urea-formaldehyde resin 48 parts, PPS8 part, EVA-g-MAH3.4 part, hollow aluminum oxide microspheres 9.6 parts, 5 parts, xylogen, talcum powder 19 parts, aluminate coupling agent 2 parts, citric acid 1.2 parts, mineral dye 0.5 part, calcium stearate 2 parts, vulkacit H 3.3 parts.
Its preparation method in the same manner as in Example 1.
After tested, the toughness of embodiment 1-6 and comparative example, hydrolytic resistance and thermotolerance are as shown in the table, wherein,
The Chinese patent of comparative example to be publication number be CN102731962A,
Toughness presses the shock strength that GB/T1043-1993 tests determinand;
Hydrolytic resistance test process is: be placed in by determinand after boiling water boils 10 hours, test its mechanical property conservation rate after being cooled to room temperature;
Thermotolerance presses the heat-drawn wire that ASTMD648 tests determinand.
As seen from the above table, shock strength of the present invention, stretching strength retentivity, flexural strength conservation rate, heat-drawn wire, all significantly better than comparative example, have good toughness, hydrolytic resistance and thermotolerance.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. urea resin matrix composite material, it is characterized in that: its component and parts by weight are: urea-formaldehyde resin 40 ~ 60 parts, PPS6 ~ 8 part, compatilizer 3 ~ 4 parts, hollow aluminum oxide microspheres 8 ~ 10 parts, toughner 2 ~ 5 parts, filler 15 ~ 20 parts, coupling agent 1 ~ 2 part, 1 ~ 2 part, solidifying agent, pigment 0.5 ~ 1 part, lubricant 1 ~ 2 part, stablizer 3 ~ 5 parts.
2. urea resin matrix composite material according to claim 1, is characterized in that: described compatilizer is EVA-g-MAH.
3. urea resin matrix composite material according to claim 1, is characterized in that: described toughner is xylogen.
4. urea resin matrix composite material according to claim 1, is characterized in that: described filler is talcum powder or calcium carbonate.
5. urea resin matrix composite material according to claim 1, is characterized in that: described coupling agent is aluminate coupling agent.
6. urea resin matrix composite material according to claim 1, is characterized in that: described solidifying agent is citric acid.
7. urea resin matrix composite material according to claim 1, is characterized in that: described pigment is mineral dye.
8. urea resin matrix composite material according to claim 1, is characterized in that: described lubricant is calcium stearate.
9. urea resin matrix composite material according to claim 1, is characterized in that: described stablizer is vulkacit H.
10. the preparation method of the urea resin matrix composite material according to claim 1 ~ 9 any one, is characterized in that: its step is as follows:
(1) hollow aluminum oxide microspheres to be dissolved in dry toluene magnetic agitation 2 hours, magnetic agitation is continued 20 hours after adding aluminate coupling agent, with ethanol purge 40 minutes after taking out, to be placed at vacuum drier 100 DEG C dry 3 hours, obtained modified aluminas tiny balloon after grinding;
(2) urea-formaldehyde resin, PPS, compatilizer are added stirrer for mixing 10 minutes together, to move in twin screw extruder temperature 160-200 DEG C, rotating speed is melt extrude under 800rpm, obtained blend composition;
(3) toughner, filler, solidifying agent, pigment, lubricant, stablizer, step (1) gained modified aluminas tiny balloon, step (2) gained blend composition put into kneader and mediated 40 minutes, dry at 70 DEG C, pulverize rear obtained molding powder;
(4) step (3) gained molding powder is put into compression molding forming machine compression molding, charge temperature is 140 DEG C, and mold temperature is 145 DEG C, and forming pressure is 5Mpa, and set time is 3 minutes, obtains urea resin matrix composite material.
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| CN105419704A (en) * | 2015-11-23 | 2016-03-23 | 苏州盖德精细材料有限公司 | 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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| CN112143246A (en) * | 2020-09-19 | 2020-12-29 | 周静 | Application method of lignin in phenolic resin molding compound |
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| Publication number | Publication date |
|---|---|
| CN105038118B (en) | 2018-04-03 |
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