CN1123599C - Process for praparing phenolic resin/clag nano composite material - Google Patents
Process for praparing phenolic resin/clag nano composite material Download PDFInfo
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- CN1123599C CN1123599C CN 01118820 CN01118820A CN1123599C CN 1123599 C CN1123599 C CN 1123599C CN 01118820 CN01118820 CN 01118820 CN 01118820 A CN01118820 A CN 01118820A CN 1123599 C CN1123599 C CN 1123599C
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Abstract
The present invention discloses a method for preparing a phenolic resin/ clay nanometer composite material, which comprises the following steps that (1), phenolic resin is melted into liquid at proper temperature; (2), 1 to 20% parts by weight of lamellar silicate clay is added into the liquid phenolic resin during stirring; (3), the mixture is continuously stirred for 10 to 200 minutes in a temperature preserving mode. The present invention directly adopts cheap natural lamellar silicate minerals as raw materials, and the natural lamellar silicate minerals have no need to be organically treated. The production technology is greatly simplified, and the production cost is reduced. The method not only is suitable for thermoplastic phenolic resin, but also is suitable for thermoplastic liquid phenolic resin, and the nanometer-grade dispersion of clay sheet layers in the resin is even and sufficient.
Description
The present invention relates to a kind of preparation method of composite nano polymer/clay material, particularly a kind of preparation method of nano-class phenolic resin/day composition.
Composite nano polymer/clay material is the emerging matrix material of a class.Because can forming nano level in polymkeric substance, disperses clay layer, so only need filler (＜5% weight) seldom that intensity, modulus, barrier property and the thermotolerance etc. of matrix material are obviously improved.Also caused the extensive concern of many Chinese scholars thus.
Melt intercalated method is a kind of important method of preparation composite nano polymer/clay material.So-called fusion intercalation is that polymkeric substance direct intercalation under molten state is entered the silicate plate interlayer, thereby obtains composite nano polymer/clay material.Composite nano polymer/clay material can be divided into two kinds in intercal type matrix material and exfoliated matrix material according to the intercalated state of polymeric matrix and layered silicate lamella.The intercal type matrix material is meant that polyalcohol intercalation enters the silicate plate interlayer, though sheet interlayer spacing is obviously increased, still basic keeping parallelism state has certain order between the lamella; And exfoliated matrix material is meant that clay layer is stripped from into monolithic layer and random dispersion fully in polymeric matrix, and this moment, clay layer and polymkeric substance can unconfinedly mix.Common exfoliated matrix material than the used clay of intercal type matrix material still less, material property is better.
For effectively expanding the sheet interlayer spacing of clay, being convenient to polymer is easy to insert between the lamella under molten state, people attempt adopting earlier various organism to the clay processing that organises, its sheet interlayer spacing is increased to some extent, it is compound organized clay and polymkeric substance to be carried out fusion intercalation again, obtains composite nano polymer/clay material.Use this method, Chinese scholars has successfully prepared multiple polymers/clay nanocomposites such as nylon/clay, PET/ clay, PS/ clay, PP/ clay, PE/ clay, epoxy resin/clay, and one of gordian technique that also therefore becomes the preparation composite nano polymer/clay material is handled in organising of clay.Nonetheless, the clay layer in wherein most of matrix materials still fails to reach fully to peel off.And dissimilar organise to handle not only make complex manufacturingization, production cost increases, and has also limited the kind of the polymkeric substance that can be used for preparing nano composite material.
Resol is very representational a kind of macromolecular material in numerous polymkeric substance, in many fields such as electronics, electrical equipment, machinery, casting, building materials, traffic, national defence, aerospace important purposes is arranged.So the research and development nano-class phenolic resin/day composition has important academic significance and economic worth.
Melt intercalated method is a kind of simple but effective method of preparation nano-class phenolic resin/day composition.But, be difficult to effectively insert between the clay class silicate lamella because the molecule of resol is three-dimensional structure more.For this reason, the method for bibliographical information all needs if you would to take off soil etc. to layered silicate and carries out the various processing that organise, and is compound with the resol fusion at high temperature of finished product again, obtain matrix material (Min Ho Choi, et al, the Chem.Mater. of fusion intercalation, 12 (10), 2977).Because adopting expensive organophilic clay is raw material, this method complex technical process, production cost is higher, and is difficult to obtain exfoliated nano-class phenolic resin/day composition.
The purpose of this invention is to provide that a kind of technological process is simple, the preparation method of the nano-class phenolic resin/day composition of low production cost.It is raw material that this method adopts natural clay of laminar silicate, the processing that need not to organise, and can obtain exfoliated nano-class phenolic resin/day composition.
The preparation method of nano-class phenolic resin/day composition of the present invention, carry out as follows:
1. resol fusion under proper temperature is in a liquid state.
2. stir the clay of laminar silicate that adds 1-20% weight part (with respect to the gross weight of resol and clay of laminar silicate) down.
3. continue insulated and stirred and promptly obtained nano-class phenolic resin/day composition in 10-200 minute.
Described resol can be novolac resin, also can be the thermoset liquid phenolic resin, can use the commercially available prod.
Described proper temperature is meant the fusion combined temp that should select for use according to different types of resol.Fusion combined temp to novolac resin is 120-180 ℃; Combined temp to the thermoset liquid phenolic resin is 30-80 ℃.
Layered silicate clay is that a class contains 80% above polynite, wilkinite, hectorite, the tired layer silicate mineral of types such as stone or vermiculite, particle diameter 200～400 orders, the specific surface area 700～800m of taking off
2/ g, interlayer has Na
+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, ion-exchange total volume (CEC) 50～200meq/100g, clay layer thickness is 0.9-1.1nm, interfloor distance is 0.8～2.1nm.
The present invention has following advantage:
1. directly adopting cheap natural layer silicate mineral is raw material, does not need its processing that organises.Simplify production technique greatly, reduced production cost.
2. present method both had been applicable to novolac resin, was applicable to the thermoset liquid phenolic resin again.Technological process is simple.The nano level of clay layer in resin is uniformly dispersed and fully.
3. the application prospect of gained nano-class phenolic resin/day composition is very wide, except that quality raising that can be used for the related various materials of traditional resol (as phenolaldehyde moulding compound, coating, tackiness agent, laminating material etc.) and improved performance, also can be used for developing new high performance composite (as friction resistance materials such as brake facing, emery wheel, gears, high-module high-strength resin/fibre composite etc.).
Matrix material typical case's XRD figure of the present invention and TEM photo are as follows:
Fig. 1 is the TEM photo of a kind of intercal type nano-class phenolic resin/day composition among the present invention.Although sheet interlayer spacing has obvious increase than the primitive soil sheet interlayer spacing, but still be multi-disc ply form.
Fig. 2 is the TEM photo of a kind of exfoliated nano-class phenolic resin/day composition of the embodiment of the invention.Can see that the clay layer spacing significantly increases, clay is dispersed in the resol body with the monolithic layer form substantially.
Fig. 3 is sodium-based montmorillonite in the embodiment of the invention (a), the XRD analysis result of a kind of intercal type resol/Nano composite material of montmorillonite (b) and a kind of exfoliated resol/Nano composite material of montmorillonite (c).Strength reduction is moved in more original polynite 001 diffraction peak position, 001 diffraction peak position of intercal type matrix material to little angular direction.001 diffraction peak completely dissolve of exfoliated matrix material illustrates that interlamellar spacing is enough big.
Fig. 4 is natural tired stone (a) and the gained resol/tired XRD analysis result who takes off stone nano composite material (b) of taking off in the embodiment of the invention.001 diffraction peak completely dissolve of gained matrix material illustrates that the tired stone interlamellar spacing of taking off is very big, forms the nano composite material of peeling off fully.
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1:
Take by weighing 95.0 gram thermoplasticity solid phenolic resins (Jinan holy well sea Butterworth chemical industry company limited, PF-1829 resin) and be put in the there-necked flask, in oil bath, be warming up to 140 ℃ and make the resin fusion.Adding 5.0 gramion total exchange capacities under stirring is the sodium-based montmorillonite clay of 100meq/100g, and insulated and stirred obtained nano-class phenolic resin/day composition in 2 hours.Matrix material is measured the d of clay through X-ray diffraction (XRD)
001The diffraction peak of interplanar distance (according to Bragg equation 2dsin θ=λ, the more little then interlamellar spacing between clay layer of the angle of diffraction peak correspondence is big more) and transmission electron microscope (TEM) observation clay layer thickness and degree of scatter.In the analysis revealed gained matrix material, clay layer reaches in novolac resin to be peeled off and fully with the nanoscale homodisperse.
Embodiment 2:
Take by weighing 98.0 gram thermoplasticity solid phenolic resins (Shandong Laiwu Resin Factory, LW-102 resin) and be put in the there-necked flask, in oil bath, be warming up to 130 ℃ and make the resin fusion.Adding 3.0 gramion total exchange capacities under stirring is the calcium-base montmorillonite clay of 80meq/100g, and insulated and stirred obtained nano-class phenolic resin/day composition in 2 hours.XRD, tem analysis show in the gained matrix material, and clay layer forms the intercal type matrix material and with the nanoscale homodisperse in novolac resin.
Embodiment 3:
Take by weighing 85.0 gram thermoplasticity solid phenolic resins (Shanghai Plastic Factory, U8101 resin) and be put in the there-necked flask, in oil bath, be warming up to 160 ℃ and make the resin fusion.Adding the ion-exchange total volume under stirring is sodium-based montmorillonite clay 15.0 grams of 120meq/100g, and insulated and stirred obtained nano-class phenolic resin/day composition in 3 hours.XRD, tem analysis show in the gained matrix material, and clay layer forms the intercal type matrix material and with the nanoscale homodisperse in novolac resin.
Embodiment 4:
Take by weighing 92.0 gram thermoplasticity solid phenolic resins (Shanghai Plastic Factory, M5082 resin) and be put in the there-necked flask, in oil bath, be warming up to 150 ℃ and make the resin fusion.Adding 8.0 gramion total exchange capacities under stirring is the sodium-based montmorillonite clay of 110meq/100g, and insulated and stirred obtained nano-class phenolic resin/day composition in 2.5 hours.XRD, tem analysis show in the gained matrix material, and clay layer reaches in novolac resin to be peeled off and fully with the nanoscale homodisperse.
Embodiment 5:
Take by weighing 98.0 gram thermoset liquid phenolic resins (Changsha resin processing plant, 2124 resins) and be put in the there-necked flask, in water-bath, be warming up to 40 ℃ resin viscosity is decreased.Adding 2.0 gramion total exchange capacities under stirring is the sodium-based montmorillonite clay of 100meq/100g, and insulated and stirred obtained the heat-reactive phenolic resin that nanoclay is filled in 1.5 hours.XRD, tem analysis show that clay layer reaches and peel off fully and with the nanoscale homodisperse in heat-reactive phenolic resin.
Embodiment 6:
Take by weighing 96.0 gram thermoset liquid phenolic resins (Hangzhou resin processing plant, 2121 resins) and place there-necked flask, in water-bath, be warming up to 50 ℃ resin viscosity is decreased.Adding 4.0 gramion total exchange capacities under stirring is that the natural tired of 50meq/100g takes off the stone clay, and insulated and stirred obtained the heat-reactive phenolic resin that nanoclay is filled in 2 hours.XRD, tem analysis show that clay layer reaches and peel off fully and with the nanoscale homodisperse in heat-reactive phenolic resin.
Embodiment 7:
Take by weighing 94.0 gram thermoset liquid phenolic resins (Jinan holy well sea Butterworth chemical industry company limited, PF-5406 resin) and be put in the there-necked flask, in water-bath, be warming up to 60 ℃ resin viscosity is decreased.Adding 6.0 gramion total exchange capacities under stirring is the sodium-based montmorillonite clay of 110meq/100g, and insulated and stirred obtained the heat-reactive phenolic resin that nanoclay is filled in 2.5 hours.XRD, tem analysis show that clay layer reaches and peel off fully and with the nanoscale homodisperse in heat-reactive phenolic resin.
Embodiment 8:
Take by weighing 90.0 gram thermoset liquid phenolic resins (Jinan holy well sea Butterworth chemical industry company limited, PF-5323 resin) and be put in the there-necked flask, in water-bath, be warming up to 60 ℃ resin viscosity is decreased.Adding 10.0 gramion total exchange capacities under stirring is the sodium-based montmorillonite clay of 110meq/100g, and insulated and stirred obtained the heat-reactive phenolic resin that nanoclay is filled in 3.0 hours.XRD, tem analysis show that clay layer reaches and peel off fully and with the nanoscale homodisperse in heat-reactive phenolic resin.
Claims (4)
1. the preparation method of a nano-class phenolic resin/day composition, carry out as follows:
1) resol fusion under proper temperature is in a liquid state;
2) stir the clay of laminar silicate that adds down with respect to the gross weight 1-20% weight part of resol and clay of laminar silicate;
3) continued insulated and stirred 10-200 minute.
2. according to the preparation method of claim 1, it is characterized in that: described resol is novolac resin or thermoset liquid phenolic resin.
3. according to the preparation method of claim 1, it is characterized in that: described proper temperature is 120-180 ℃ to novolac resin; To the thermoset liquid phenolic resin is 30-80 ℃.
4. according to the preparation method of claim 1, it is characterized in that: layered silicate clay is that a class contains 80% above polynite, wilkinite, hectorite, the tired layer silicate mineral of types such as stone or vermiculite that takes off, particle diameter 200～400 orders, specific surface area 700～800m
2/ g, interlayer has Na
+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, ion-exchange total volume 50～200meq/100g, clay layer thickness are 0.9-1.1nm, and interfloor distance is 0.8～2.1nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118820 CN1123599C (en) | 2001-06-18 | 2001-06-18 | Process for praparing phenolic resin/clag nano composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118820 CN1123599C (en) | 2001-06-18 | 2001-06-18 | Process for praparing phenolic resin/clag nano composite material |
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| CN1392196A CN1392196A (en) | 2003-01-22 |
| CN1123599C true CN1123599C (en) | 2003-10-08 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293980B (en) * | 2007-05-30 | 2010-09-29 | 北京中科普惠科技发展有限公司 | Thermoplastic polyalcohol/clay soil nano-composite material, preparation method and application thereof |
| CN101139172B (en) * | 2007-08-22 | 2010-11-03 | 北京玻钢院复合材料有限公司 | Glass fiber screen cloth immersing glue solution for grinding wheel reinforcement and initial rinsing method |
| DE102012219303A1 (en) * | 2011-11-17 | 2013-05-23 | Schaeffler Technologies AG & Co. KG | Friction and/or sliding liner, useful in brake disc, comprises plastic matrix containing graphite as filler, where the matrix in addition to the graphite comprises nanofiller and the graphite is combined with the nanofiller as microfiller |
| CN102766316B (en) * | 2012-07-31 | 2013-09-25 | 浙江大学 | Sisal hemp glass fiber composite reinforced organosilicone modified phenolic aldehyde molding material and preparation method thereof |
| CN102766317B (en) * | 2012-07-31 | 2013-09-25 | 浙江大学 | Organosilicone modified phenolic aldehyde injection molding material and preparation method thereof |
| CN102775725B (en) * | 2012-07-31 | 2013-10-30 | 浙江大学 | Glass fiber reinforced organic silicon modified phenolic molding material and preparation method thereof |
| CN106009487B (en) * | 2015-03-24 | 2017-10-31 | 泉州市中研智能机电研究院有限公司 | A kind of preparation method of phenolic resin-base composite |
| CN107540804B (en) * | 2017-08-31 | 2019-12-10 | 武汉科技大学 | Phenolic resin for carbon-containing refractory material and preparation method thereof |
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