CN102766316A - 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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- CN102766316A CN102766316A CN2012102692775A CN201210269277A CN102766316A CN 102766316 A CN102766316 A CN 102766316A CN 2012102692775 A CN2012102692775 A CN 2012102692775A CN 201210269277 A CN201210269277 A CN 201210269277A CN 102766316 A CN102766316 A CN 102766316A
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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 a preparation 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 is long 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, has cheaply, and mechanical property is excellent; 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 said 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 a kind of high-temperature-resistant inorganic fibre enhanced injection phenolic moulding plastics; This phenolaldehyde moulding compound forms as material prepns such as matrix mixing inorganic reinforcement, solidifying agent with common novolac resin; Owing to use common resol as matrix, though mechanical property and resistance toheat increase, 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 spun glass to mix, added that the viscosity of common resol own is bigger with common phenolic aldehyde, bigger to the screw rod wearing and tearing.
Publication number is the preparation method that the USP of US6440255B1 discloses a kind of fast setting phenolaldehyde moulding compound; Mainly quicken its solidification rate, but its overall performance of material after solidifying is compared not too big raising with common phenolaldehyde moulding compound through adding Z 150PH or long carbon chain acrylate class material in moulding compound.
Publication number is that the USP of US6838509B2 discloses a kind of phenolaldehyde moulding compound; Adding through 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 spun glass and cotton fibre simultaneously, adopt the nano grade inorganic filler, the intensity of material and anti-shrinkability 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 spun glass 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 spun glass, 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 adjacent at-OH, 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, toughness and the thermotolerance all moulding compound than common resol preparation are high, in addition; Described sisal fibers also significantly improves its volume specific resistance simultaneously at the flexible of enhancement mode plastics, and spun glass 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 insulating property, toughness and the thermotolerance of described organic-silicon-modified novolac resin, and then improves insulating property, toughness and the thermotolerance of described phenolaldehyde moulding compound, 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, and 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 further is preferably 1～5 integer, and described R further is preferably hydrogen, C
1～C
5Alkyl or C
1～C
5Alkoxyl group.
The length 1-10mm of described spun glass, the length of described sisal fibers is 1-10mm, the weight ratio of described spun glass and sisal fibers is 1: 0.1～10.Wherein, the increase of spun glass ratio helps improving the flexural strength and the shock strength of said phenolaldehyde moulding compound, and the increase of sisal fibers ratio helps improving the toughness and the insulating property of said phenolaldehyde moulding compound.
Stopping composition among the present invention is preferably at least a in mica powder, lime 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 Triple Pressed Stearic Acid, Zinic stearas, furfural, terepthaloyl moietie and the acetate bis-stearamides; Further be preferably Zinic stearas, can play better demoulding effect to phenolaldehyde moulding compound of the present invention this moment.
Described tinting material can be so that moulding compound presents distinct colors; And then the needs of suitable different occasions; Among the present invention; Described tinting material is preferably at least a in nigrosine, red iron oxide and the red, and 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 epoxy resin; 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 further is preferably urotropine.
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 spun glass, comprising:
(1) batch mixing: take by weighing described organic-silicon-modified novolac resin, spun glass, 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 the mixing completion, 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 following: 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 reaction kettle, 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 a 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), make the phenolaldehyde moulding compound that makes have better shock strength and flexural strength through the adding of spun glass;
(4), make the phenolaldehyde moulding compound that makes have better toughness and insulating property through the adding of sisal fibers.
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: (164kg 1000mol) adds synthesis reaction vessel with Platinic chloride 15g, stirs and is warming up to 55-65 ℃ with Eugenol; With 1,1,3; 3-tetramethyl disiloxane (67kg; 500mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished in lasting 2-3 hour more promptly to process organosilicon modifier, and the structural formula and the nuclear magnetic spectrogram of this organosilicon modifier are as shown in Figure 1; Productive rate 93%, the structural formula and the nuclear magnetic spectrogram of this organosilicon modifier 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 to drip quality percentage composition 37% formalin 45kg insulation 1.5 hours muddy to system, 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: (82kg 500mol) adds synthesis reaction vessel with Platinic chloride 9g, stirs and is warming up to 55-65 ℃ with Eugenol; With 1,1,3; (33.5kg 250mol) drips in the reaction kettle 3-tetramethyl disiloxane in batches, keeps temperature not to be higher than 80 ℃; Reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 94% again in lasting 2-3 hour.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 10kg that processes 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 to drip quality percentage composition 37% formalin 55kg insulation 2 hours muddy to system, 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: (133kg 1000mol) adds synthesis reaction vessel with Platinic chloride 15g, stirs and is warming up to 55-65 ℃ with the 2-allyl phenol; With 1,1,3; 3-tetramethyl disiloxane (67kg; 500mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 91% again in lasting 2-3 hour.
(2) preparation of organic-silicon-modified novolac resin: phenol 80kg, the organosilicon modifier 10kg that processes 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 to drip quality percentage composition 37% formalin 45kg insulation 2 hours muddy to system, 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 1 with Eugenol; 1,3,3,5; 5,7,7-prestox tetrasiloxane (99.7kg; 352mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, and reaction proceeds to and after the phenomenon that heats up stops, finished promptly to process organosilicon modifier, productive rate 95% again in lasting 2-3 hour.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 15kg that processes 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 to drip quality percentage composition 37% formalin 55kg insulation 2 hours muddy to system, 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 ℃; (256.6kg, 352mol) dropping advances to keep in the reaction kettle temperature not to be higher than 80 ℃ in batches, reacts to proceed to and after the phenomenon that heats up stops, finishes promptly to process organosilicon modifier again in lasting 2-3 hour with two decamethyls, ten siloxanes.
(2) preparation of organic-silicon-modified novolac resin: phenol 100kg, the organosilicon modifier 20kg that processes 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 to drip quality percentage composition 37% formalin 55kg insulation 2 hours muddy to system, 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 is relatively seen 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 spun glass phenolaldehyde moulding compound
Embodiment 1
With promptly getting the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass pulverizing after 30 minutes in the refining of 130 ℃ of lower rolls in two roller mills behind the said components mixing.
Embodiment 2
With promptly getting the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass 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 |
With promptly getting the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass 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 the foregoing description 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 |
Performance according to embodiment and reference example gained material can know, 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 used iodometric determination in accordance with GB GB-T7130-1986.
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 said 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 (9)
1. organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass 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 or more adjacent at-OH, or contraposition on any substituting group, n is 1～500 integer.
2. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 1 is characterized in that described n is 1～50 integer, and R is selected from hydrogen, alkyl or alkoxyl group.
3. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 2 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.
4. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 1; It is characterized in that; The length 1-10mm of described spun glass, the length of described sisal fibers is 1-10mm, the weight ratio of described spun glass and sisal fibers is 1: 0.1～10.
5. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 1 is characterized in that, described stopping composition is at least a in mica powder, lime carbonate, talcum powder and the silica flour.
6. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 1 is characterized in that, described releasing agent is at least a in Triple Pressed Stearic Acid, Zinic stearas, furfural, terepthaloyl moietie and the acetate bis-stearamides.
7. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass according to claim 1 is characterized in that, described tinting material is at least a in nigrosine, red iron oxide and the red.
8. the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of sisal hemp spun glass 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 epoxy resin.
9. the preparation method of the organic-silicon-modified phenolaldehyde moulding compound of the compound enhancing of the arbitrary described sisal hemp spun glass of claim 1～8 is characterized in that, comprising:
(1) batch mixing: take by weighing described organic-silicon-modified novolac resin, spun glass, 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 the mixing completion, obtains described phenolaldehyde moulding compound.
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| CN103628307A (en) * | 2013-12-11 | 2014-03-12 | 山东科技大学 | Method for improving heat resistance of sisal fibers |
| CN103897416A (en) * | 2014-03-26 | 2014-07-02 | 浙江嘉民塑胶有限公司 | Phenolic molding plastic 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 |
| CN111019217A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Nano composite polymer material |
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| CN103510424A (en) * | 2013-09-11 | 2014-01-15 | 淮北市蒋疃民和新型建材有限责任公司 | Modified limestone powder for producing wallpapers |
| 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 |
| CN103628307A (en) * | 2013-12-11 | 2014-03-12 | 山东科技大学 | Method for improving heat resistance of sisal fibers |
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| 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 |
| CN111019217A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Nano composite polymer material |
| CN111019217B (en) * | 2019-12-23 | 2021-01-19 | 浙江大学 | Nano composite polymer material |
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