CN102766316B - Sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material and preparation method thereof - Google Patents
Sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material which comprises 35-70% of organosilicone modified thermoplastic phenolic resin, 5-45% of glass fiber and sisal hemp mixed fiber, 5-45% of packing material, 0.5-3% of demolding agent, 0.25-1.5% of coloring agent and 2-10% of curing agent. The invention further provides apreparation method of the sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material. The sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material is prepared by mixing the components, smashing or granulating and other working procedures. The phenolic aldehyde molding material prepared by using the method islong in storage time, not apt to become damp, excellent in weather fastness, small in relative density and low in production cost; and the cured material is excellent in toughness and heat resistance. Plastic parts made of the organosilicone modified phenolic aldehyde molding material have the characteristics of being long in storage time, good in toughness, small in relative density, and excellent in heat resistance.
Description
Technical field
The present invention relates to the phenolaldehyde moulding compound field, relate in particular to a kind of organic-silicon-modified phenolaldehyde moulding compound and preparation method thereof.
Background technology
Phenolaldehyde moulding compound is to be the thermoset plastic material of main raw material preparation with novolac resin and other stopping composition, have cheap, the mechanical property excellence, good insulation preformance, the characteristics that moulding is simple and efficient are widely used in military project, electric component, instrument, fields such as building.Defectives such as but such material also existing property is crisp, is difficult for storing, and resistance toheat is limited.
Notification number is that the Chinese patent of CN1175042C discloses the injection phenolic moulding plastics that a kind of high-temperature-resistant inorganic fibre strengthens, this phenolaldehyde moulding compound with common novolac resin as matrix mixing inorganic reinforcement, material preparations such as solidifying agent form, owing to use common resol as matrix, though mechanical property and resistance toheat increase, but the degree that improves is limited, and mechanical property and resistance toheat in order to improve moulding compound, used a large amount of inorganic fibres such as glass fibre to mix with common phenolic aldehyde, add that the viscosity of common resol own is bigger, bigger to the screw rod wearing and tearing.
Publication number is the preparation method that the United States Patent (USP) of US6440255B1 discloses a kind of fast setting phenolaldehyde moulding compound, mainly accelerate its solidification rate by adding polyvinyl alcohol or long carbon chain acrylate class material in moulding compound, but its overall performance of material after solidifying is compared not too big raising with common phenolaldehyde moulding compound.
Publication number is that the United States Patent (USP) of US6838509B2 discloses a kind of phenolaldehyde moulding compound, adding by organic clay makes the thermotolerance of material and physical strength get a promotion, but meanwhile because the existence of clay makes that the loss of production unit is bigger, and the adding of organic clay improved cost, lacks competitiveness on such moulding material price.
Publication number is that the Chinese patent of CN101974199A discloses a kind of low contraction phenolaldehyde moulding compound, with the thermoset linear phenolic resin as matrix, add glass fibre and cotton fibre simultaneously, adopt the nano grade inorganic filler, intensity and the anti-shrinkability of material are promoted comprehensively, but owing to use the thermoset linear phenolic resin as matrix, the phenolaldehyde moulding compound that obtains is difficult to permanent storage.
Summary of the invention
The invention provides organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of a kind of sisal hemp glass fibre and preparation method thereof, it is long that resulting phenolaldehyde moulding compound has the storage time, the advantage of insulating property, toughness and Good Heat-resistance.
The organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of a kind of sisal hemp glass fibre, weight percent consists of:
The structure of described organic-silicon-modified novolac resin is suc as formula shown in (I):
In the formula (I), Novolac
1And Novolac
2Be positioned at-ortho position or the contraposition of OH, represent the novolac resin segmented structure, R be one or more-OH neighbour, or contraposition on any substituting group, n is 1～500 integer.
Among the present invention, the common novolac resin of the viscosity ratio of described organic-silicon-modified novolac resin is low, and energy consumption is low in the described phenolaldehyde moulding compound process of preparation, and is little to the screw rod wearing and tearing; Described organic-silicon-modified novolac resin is moisture-sensitive not, and water-absorbent and weathering resistance are obviously improved than common resol, and the storage time is long; And the Si-O bond structure that contains similar inorganic silicate in the described organic-silicon-modified novolac resin, bond energy is bigger than C-C key, the insulativity of the phenolaldehyde moulding compound that makes, the moulding compound height that toughness and thermotolerance all prepare than common resol, in addition, described sisal fibers also significantly improves its volume specific resistance in the toughness of enhancement mode plastics, glass fibre then can effectively improve the mechanical property of molding product.
As preferably, the weight percent of described phenolaldehyde moulding compound consists of:
Among the present invention, the increase of described n value can improve the insulating property of described organic-silicon-modified novolac resin, toughness and thermotolerance, and then improve the insulating property of described phenolaldehyde moulding compound, toughness and thermotolerance, but the increase of n value also can make the viscosity of described organic-silicon-modified novolac resin increase, cause energy consumption increase in preparation phenolaldehyde moulding compound process, increasing is to the wearing and tearing of screw rod, described n is preferably 1～50 integer, at this moment, consider the cost of raw material and the complexity of organic-silicon-modified novolac resin preparation, described R is preferably hydrogen, alkyl or alkoxyl group.Described n is 1～5 integer more preferably, and described R is hydrogen, C more preferably
1～C
5Alkyl or C
1～C
5Alkoxyl group.
The length 1-10mm of described glass fibre, the length of described sisal fibers is 1-10mm, the weight ratio of described glass fibre and sisal fibers is 1: 0.1～10.Wherein, the increase of glass fibre ratio is conducive to improve flexural strength and the shock strength of described phenolaldehyde moulding compound, and the increase of sisal fibers ratio is conducive to improve toughness and the insulating property of described phenolaldehyde moulding compound.
Stopping composition among the present invention is preferably at least a in mica powder, calcium carbonate, talcum powder and the silica flour, and described stopping composition joins and plays a part skeleton in the phenolaldehyde moulding compound, can increase the modulus in flexure of described phenolaldehyde moulding compound.
Described releasing agent can prevent that described phenolaldehyde moulding compound is bonded to die surface, described releasing agent is preferably at least a in stearic acid, Zinic stearas, furfural, ethylene glycol and the acetic acid bis-stearamides, more preferably Zinic stearas can play better demoulding effect to phenolaldehyde moulding compound of the present invention at this moment.
Described tinting material can be so that moulding compound presents distinct colors, and then be fit to the needs of different occasions, among the present invention, described tinting material is preferably at least a in nigrosine, red iron oxide and the red, these several based colorants and described organic-silicon-modified novolac resin consistency are good, and have good dispersive ability.
Among the present invention, described solidifying agent is preferably at least a in urotropine, solid Resol type resol, liquid Resol type resol and the Resins, epoxy, the adding of solidifying agent can be so that described moulding compound forms crosslinking structure, improve insulating property, flexural strength and the shock strength of moulding compound, described solidifying agent is urotropine more preferably.
The present invention also provides the preparation method of the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of a kind of described sisal hemp glass fibre, comprising:
(1) batch mixing: take by weighing described organic-silicon-modified novolac resin, glass fibre, sisal fibers, stopping composition, releasing agent, tinting material, solidifying agent, under 20～30 ℃ of temperature, mix obtaining uniform powder-material in 10～40 minutes;
(2) mixing: under 110-130 ℃ of temperature, the powder-material that step (2) is obtained carries out mixing, after mixing the finishing, obtains described phenolaldehyde moulding compound.
Wherein, the structure of described organosilicon modifier is suc as formula shown in (II):
In the formula (II), n and R and formula (I) adapt.
Wherein, in weight part, phenol: organosilicon modifier is 1.63～33.32: 1; Massfraction 37% formalin: phenol is 0.56～0.78: 1.
Described organosilicon modifier preparation method is as follows: allyl group fragrance phenol and catalyzer are added synthesis reaction vessel, stirring is warming up to 55～65 ℃, the methyl hydrogen-containing siloxane dripped into keep temperature not to be higher than 80 ℃ in the reactor, the feed components mol ratio is every mole of methyl hydrogen-containing siloxane institute hydrogen atoms: allyl group fragrance phenol: catalyzer is 1: 1: (6 * 10
-5～9 * 10
-5), reaction continues end in 2-3 hour after proceeding to the termination of intensification phenomenon again, and described catalyzer is Pt salt, comprises organic salt and the inorganic salt of Pt.
Wherein, the structure of described allyl group fragrance phenol is suc as formula shown in (III):
The structure of described methyl hydrogen-containing siloxane is suc as formula shown in (IV):
N and formula (I) in R in the formula (III) and the formula (IV) adapt.
Compare with prior art, beneficial effect of the present invention is embodied in:
(1) use the organic silicon modified phenolic resin to replace common resol, viscosity is littler, and energy consumption is littler in the preparation process, is not easy simultaneously equipment is caused wearing and tearing;
(2) use the organic silicon modified phenolic resin to replace common resol, the phenolaldehyde moulding compound that obtains is moisture-sensitive not, and the shelf time is longer;
(3) by the adding of glass fibre, make the phenolaldehyde moulding compound that makes have better shock strength and flexural strength;
(4) by the adding of sisal fibers, make the phenolaldehyde moulding compound that makes have better toughness and insulating property.
Description of drawings
The nuclear magnetic spectrogram of the Eugenol type organosilicon modifier that Fig. 1 obtains for feedstock production example 1.
Embodiment
Feedstock production example 1
(1) preparation of organosilicon modifier: with Eugenol (164kg, 1000mol) add synthesis reaction vessel with Platinic chloride 15g, stirring is warming up to 55-65 ℃, with 1,1,3,3-tetramethyl disiloxane (67kg, 500mol) dropping advances to keep in the reactor temperature not to be higher than 80 ℃ in batches, reaction proceeds to and finished namely to make organosilicon modifier again in lasting 2-3 hour after the phenomenon that heats up stops, the structural formula of this organosilicon modifier and nuclear magnetic spectrogram as shown in Figure 1, productive rate 93%, the structural formula of this organosilicon modifier and nuclear magnetic spectrogram are as shown in Figure 1.
(2) preparation of organic-silicon-modified novolac resin: the organosilicon modifier 10kg of phenol 80kg, preparation is as stated above added synthesis reaction vessel, heat up and stir, add an amount of oxalic acid and regulate pH＜2, temperature rises to about 85 ℃ and drips quality percentage composition 37% formalin 45kg insulation 1.5 hours to the system muddiness, and decompression vacuum pumping dewaters and goes back up to 85 ℃ to system temperature and stop heating and obtain organic-silicon-modified novolac resin under heated condition then.
Nuclear magnetic data:
1H NMR (500MHz, DMSO-d6, TMS): δ=0.4 (12H, Si-CH
3), 1.5 (4H, Si-CH
2-), 1.8 (4H, Si-C-CH
2-), 2.6 (4H, Si-C-C-CH
2-), 3.5 (6H, Ar-O-CH
3) 3.6-3.8 (72H, Ar-CH
2-Ar), 4.55-4.80 (22H, Ar-CH
2-O-CH
2-Ar), and 6.80-7.21 (106H, Ar-H).
Feedstock production example 2
(1) preparation of organosilicon modifier: with Eugenol (82kg, 500mol) add synthesis reaction vessel with Platinic chloride 9g, stirring is warming up to 55-65 ℃, with 1,1,3, (33.5kg 250mol) drips in the reactor 3-tetramethyl disiloxane in batches, keeps temperature not to be higher than 80 ℃, reaction proceeds to and finished namely to make organosilicon modifier, productive rate 94% again in lasting 2-3 hour after the phenomenon that heats up stops.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 10kg that makes are as stated above added synthesis reaction vessel, add about oxalic acid regulation system pH to 2, heat up and stir, temperature rises to about 85 ℃ and drips quality percentage composition 37% formalin 55kg insulation 2 hours to the system muddiness, and decompression vacuum pumping dewaters and goes back up to 85 ℃ to system temperature and stop heating and obtain organic-silicon-modified novolac resin under heated condition then.
Nuclear magnetic data:
1H NMR (500MHz, DMSO-d6, TMS): δ=0.4 (12H, Si-CH
3), 1.5 (4H, Si-CH
2-), 1.8 (4H, Si-C-CH
2-), 2.6 (4H, Si-C-C-CH
2-), 3.5 (6H, Ar-O-CH
3) 3.6-3.8 (73H, Ar-CH
2-Ar), 4.55-4.80 (20H, Ar-CH
2-O-CH
2-Ar), and 6.80-7.21 (102H, Ar-H).
Feedstock production example 3
(1) preparation of organosilicon modifier: with 2-allyl phenol (133kg, 1000mol) add synthesis reaction vessel with Platinic chloride 15g, stirring is warming up to 55-65 ℃, with 1,1,3,3-tetramethyl disiloxane (67kg, 500mol) dropping advances to keep in the reactor temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and finished namely to make organosilicon modifier, productive rate 91% again in lasting 2-3 hour after the phenomenon that heats up stops.
(2) preparation of organic-silicon-modified novolac resin: phenol 80kg, the organosilicon modifier 10kg that makes are as stated above added synthesis reaction vessel, add about oxalic acid regulation system pH to 2, heat up and stir, temperature rises to about 85 ℃ and drips quality percentage composition 37% formalin 45kg insulation 2 hours to the system muddiness, and decompression vacuum pumping dewaters and goes back up to 85 ℃ to system temperature and stop heating and obtain organic-silicon-modified novolac resin under heated condition then.
Nuclear magnetic data:
1H NMR (500MHz, DMSO-d6, TMS): δ=0.4 (12H, Si-CH
3), 1.5 (4H, Si-CH
2-), 1.8 (4H, Si-C-CH
2-), 2.6 (4H, Si-C-C-CH
2-), 3.6-3.8 (80H, Ar-CH
2-Ar), 4.55-4.80 (16H, Ar-CH
2-O-CH
2-Ar), and 6.80-7.21 (112H, Ar-H).
Feedstock production example 4
(1) preparation of organosilicon modifier: (82kg 500mol) adds synthesis reaction vessel with Platinic chloride 9g, stirs and is warming up to 55-65 ℃ with Eugenol, with 1,1,3,3,5,5,7,7-prestox tetrasiloxane (99.7kg, 352mol) dropping advances to keep in the reactor temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and finished namely to make organosilicon modifier, productive rate 95% again in lasting 2-3 hour after the phenomenon that heats up stops.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 15kg that makes are as stated above added synthesis reaction vessel, add about oxalic acid regulation system pH to 2, heat up and stir, temperature rises to about 85 ℃ and drips quality percentage composition 37% formalin 55kg insulation 2 hours to the system muddiness, and decompression vacuum pumping dewaters and goes back up to 135 ℃ to system temperature and stop heating and obtain organic-silicon-modified novolac resin under heated condition then.
Nuclear magnetic data:
1H NMR (500MHz, DMSO-d6, TMS): δ=0.4 (12H, Si-CH
3), 1.5 (4H, Si-CH
2-), 1.8 (4H, Si-C-CH
2-), 2.6 (4H, Si-C-C-CH
2-), 3.5 (6H, Ar-O-CH
3) 3.6-3.8 (70H, Ar-CH
2-Ar), 4.55-4.80 (10H, Ar-CH
2-O-CH
2-Ar), and 6.80-7.21 (95H, Ar-H).
Feedstock production example 5
(1) preparation of organosilicon modifier: with Eugenol (82kg, 500mol) add synthesis reaction vessel with Platinic chloride 9g, stirring is warming up to 55-65 ℃, with two decamethyls, ten siloxanes (256.6kg, 352mol) dropping advances to keep in the reactor temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and finished namely to make organosilicon modifier again in lasting 2-3 hour after the phenomenon that heats up stops.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 20kg that makes are as stated above added synthesis reaction vessel, add about oxalic acid regulation system pH to 2, heat up and stir, temperature rises to about 85 ℃ and drips quality percentage composition 37% formalin 55kg insulation 2 hours to the system muddiness, and decompression vacuum pumping dewaters and goes back up to 135 ℃ to system temperature and stop heating and obtain organic-silicon-modified novolac resin under heated condition then.
Nuclear magnetic data:
1H NMR (500MHz, DMSO-d6, TMS): δ=0.4 (12H, Si-CH
3), 1.5 (4H, Si-CH
2-), 1.8 (4H, Si-C-CH
2-), 2.6 (4H, Si-C-C-CH
2-), 3.5 (6H, Ar-O-CH
3) 3.6-3.8 (70H, Ar-CH
2-Ar), 4.55-4.80 (10H, Ar-CH
2-O-CH
2-Ar), and 6.80-7.21 (106H, Ar-H).
The above-mentioned resol performance that makes relatively sees Table 1
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
|
| Free phenol, % | 3.4 | 3.5 | 4.1 | 3.6 | 3.8 |
| Gel time, s | 29 | 36 | 41 | 39 | 37 |
The preparation of the compound enhancing organosilicon of sisal hemp glass fibre phenolaldehyde moulding compound
Embodiment 1
To namely get the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre pulverizing after 30 minutes in the refining of 130 ℃ of lower rolls in two roller mills behind the said components mixing.
Embodiment 2
To namely get the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre pulverizing after 35 minutes in the refining of 125 ℃ of lower rolls in two roller mills behind the said components mixing.
Reference example 1
| Form | Concrete raw material | Weight percentage % | |
| Resol | Common novolac resin | 35 | |
| Glass | Chopped glass fiber | 35 | |
| Stopping composition | Mica powder | 22 | |
| Releasing agent | Zinic stearas | 2 | |
| Solidifying | Urotropine | 5 | |
| Tinting material | Nigrosine | 1 |
To namely get the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre pulverizing after 40 minutes in the refining of 120 ℃ of lower rolls in two roller mills behind the said components mixing.
The phenolic aldehyde injection molding material performance that above-described embodiment makes relatively sees the following form 2:
Table 2
| Performance | Embodiment 1 | Embodiment 2 | Reference example 1 |
| Flexural strength Mpa | 96.3 | 98.7 | 83.5 |
| Shock strength, kJ/m 2 | 3.43 | 2.97 | 2.65 |
| Heat-drawn wire, ℃ | 204 | 199 | 189 |
| Volume specific resistance, Ω m | 2.14×10 14 | 1.23×10 14 | 4.56×10 12 |
According to the performance of embodiment and reference example gained material as can be known, organosilicon modifier be introduced in effective raising flexural strength, shock strength and heat-drawn wire the time, its volume specific resistance also gets a promotion.
Performance characterization method:
1, free phenol content is abideed by GB GB-T7130-1986 iodometric determination.
2, resin gel timing: get the 4.5g resin and add the 0.5g urotropine, be positioned over after grinding evenly on 150 ± 1 ℃ the hot iron plate and shakeout rapidly with glass stick, be gel time writing time till lifting no longer silk from whole fusing timing to glass stick, surveys and average for three times.
3, shock strength is pressed GBT1043.1-2008 mensuration, and flexural strength is pressed GBT 9341-2000 and measured, batten size 80 * 10 * 4 (mm).
4, volume specific resistance is pressed GBT1410-2006 mensuration, and specimen preparation is referring to anti-impact batten preparation method, and wherein sample size is the cake of diameter 100mm thickness 3mm.
5, heat-drawn wire is pressed GBT9341-2000 and is measured the batten preparation method:
In described ratio material is practiced the injection moulding sample preparation of (140 ℃ of temperature) back, 160 ℃ of mould temperature, pressure 25MPa, dwell time 1min/mm, batten size 80 * 10 * 4 (mm) at two roller top rolls.
Claims (8)
1. organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre is characterized in that weight percent consists of:
The structure of described organic-silicon-modified novolac resin is suc as formula shown in (I):
In the formula (I), Novolac
1And Novolac
2Be positioned at-ortho position or the contraposition of OH, represent the novolac resin segmented structure, R be one-OH neighbour, or contraposition on substituting group, n is 1～50 integer;
R is selected from hydrogen, alkyl or alkoxyl group.
2. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1 is characterized in that, described n is 1～5 integer, and R is selected from hydrogen, C
1～C
5Alkyl or C
1～C
5Alkoxyl group.
3. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1, it is characterized in that, the length 1-10mm of described glass fibre, the length of described sisal fibers is 1-10mm, the weight ratio of described glass fibre and sisal fibers is 1: 0.1～10.
4. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1 is characterized in that, described stopping composition is at least a in mica powder, calcium carbonate, talcum powder and the silica flour.
5. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1 is characterized in that, described releasing agent is at least a in stearic acid, Zinic stearas, furfural and the ethylene glycol.
6. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1 is characterized in that, described tinting material is at least a in nigrosine, red iron oxide and the red.
7. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp glass fibre according to claim 1, it is characterized in that described solidifying agent is at least a in urotropine, solid Resol type resol, liquid Resol type resol and the Resins, epoxy.
8. the preparation method of the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of the arbitrary described sisal hemp glass fibre of claim 1～7 is characterized in that, comprising:
(1) batch mixing: take by weighing described organic-silicon-modified novolac resin, glass fibre, sisal fibers, stopping composition, releasing agent, tinting material, solidifying agent, under 20～30 ℃ of temperature, mix obtaining uniform powder-material in 10～40 minutes;
(2) mixing: under 110-130 ℃ of temperature, the powder-material that step (2) is obtained carries out mixing, after mixing the finishing, obtains described phenolaldehyde moulding compound.
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| CN103510424B (en) * | 2013-09-11 | 2016-08-17 | 淮北市蒋疃民和新型建材有限责任公司 | A kind of modified lime stone flour for making wallpaper |
| CN103628307B (en) * | 2013-12-11 | 2015-05-06 | 山东科技大学 | Method for improving heat resistance of sisal fibers |
| CN103897416B (en) * | 2014-03-26 | 2016-05-18 | 浙江嘉民塑胶有限公司 | A kind of phenolaldehyde moulding compound and preparation method thereof |
| CN105348728A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | A wear-resistant heat-resisting environmental-friendly material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392196A (en) * | 2001-06-18 | 2003-01-22 | 中国科学院化学研究所 | Process for praparing phenolic resin/clag nano composite material |
| CN102337002A (en) * | 2011-06-17 | 2012-02-01 | 莱州市顺利达电子材料有限公司 | Organic silicon modified phenolic resin encapsulating material and preparation method and usage thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392196A (en) * | 2001-06-18 | 2003-01-22 | 中国科学院化学研究所 | Process for praparing phenolic resin/clag nano composite material |
| CN102337002A (en) * | 2011-06-17 | 2012-02-01 | 莱州市顺利达电子材料有限公司 | Organic silicon modified phenolic resin encapsulating material and preparation method and usage thereof |
Non-Patent Citations (2)
| Title |
|---|
| 左小华等.有机硅改性热塑性酚醛树脂制备的研究.《广东化工》.2011,第38卷(第7期),第16-17页. |
| 有机硅改性热塑性酚醛树脂制备的研究;左小华等;《广东化工》;20111231;第38卷(第7期);第16-17页 * |
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