2006-2007 world phenolic resin and plastics industry progress
2009-11-25 09:22:34 Author: China phenolic resin net : http://www.pf-e.cn
Zhu Yongmao, Yanrong Zhong, Liu Yong, Yang Wei
(Shanghai Euro-Asian Synthetic Material Co., Ltd. Shanghai 201102)
Abstract: This paper informed of production, consumption, corporate mergers and restructuring of production of phenolic resin and plastic , and expansion of raw materials phenol between2006-2007. And introduced technical progress of phenolic molding compound, phenolic resin composite materials and curing mechanism of phenolic resin.
Key words: phenolic resin; production; consumption; phenol; molding compound; composite materials
Document code: A Article ID :1002-7432 (2008) 03-0041-03
Phenolic resin as the oldest synthetic resin, because of its high mechanical strength, good heat resistance, flame retardant, low toxicity, low smoke, blends with other polymers to achieve high performance, is widely used in molding compounds, coatings, friction materials, foundry resins, adhesives, foam, semiconductor packaging materials, photoresists and other fields.
May 2007, the United States Advanced Materials Science and Technology Association (SAMPE) held 63th annual meeting, and global phenolic resin Association (GPRA) Annual Meeting was held in Kuala Lumpur, Malaysia in March 2008. Both meetings gave positive comments to the development prospects of the phenolic resin and plastic.
1.Production and market situation
The required amount of phenol resin around the world:
The world total demand for Phenol was 8.586 million t, of which for the phenolic resin 3.215 million t, accounting for 37.4% of the total in 2007.
According to statistics, phenolic resin consumption in recent years and forecasted consumption in 2009 is as follows:
U.S. 2,051,000t, Western Europe 370 600t, Japan 341 000t, China 450 000t, others 802 400t, total 4,015,000t.
U.S. 2.07 milliont, Western Europe 411 000t, Japan 402 000t, China 684 000t, the other 1.175 milliont, a combined 4.744 million t. It is a growth of 15.4% than 2006.
Japan’s 2006 total production of phenolic resin was 283 600t, in which molding 35 500t, laminated materials 19 400 t, wood adhesives 78000 t, other applications including the casting, friction material, fibers, etc. 150 000t [2 ].
In recent years, major international phenolic resin companies carried out major reorganization and merger:
John R. Bolton, the U.S. chemical company acquired U.S. RPP and RSM Company. 2005 the company also acquired the German Berkeley, set up the world’s largest manufacturer of thermosetting resin — Hexion Specialty Chemical Inc.;
Japan’s Sumitomo Bakelite Company acquired the U.S. Company Durez and Belgium Fenkelaite;
Schenectady International, Inc. reached an agreement with the French CACE, exchange CACE’s phenolic Division ;
United States’ Georgia Pacific Corporation held 30% of the shares of South Korea’s Kolon Chemical (Suzhou).
Currently, the world’s major phenolic resin companies are U.S. Hexion, Occidcntal chemical Ltd, Schenectady Ltd, Plastics Engineering. Co, Gevrgia-Pacific Ltd; Japan’s Sumitomo Chemical, Matsushita Electric, Dainippon Ink Co., Ltd., Hitachi Chemical, Asahi Industries, Ltd .
Driven by the rapid development of the auto industry, metallurgy,and electronic consumer goods, demand to the phenolic resin increased in molding, casting, refractory materials, electrical materials, electronics and other new areas.PF has been involved in the application of molding materials, casting materials, refractories, rubber, friction materials, abrasive grinding, packaging materials, laminates, fiber reinforced composites, phenolic foam and many other fields, covering most fields of the national economy and national defense industry and other fields. The world production of phenolic resin expanded from some 200，000t of the1950 years to 4.015 million ton in 2006. And it is expected the global phenolic resin industry will grow at 7% the next few years.
The development of phenolic resin and phenol production and supply capacity are closely related. According to statistics, in 2006 the production capacity for phenol plant was 8.756 million t: of which
the United States SUNOCO, Shell, INEOS Phenol, GE, Georgia Gulf, Dow totaled 2,831,000 t;
Western Europe, INEOS Phenol, Polimeri, Ertisa, Borealis and others totaled 2,420,000 t;
Japan, Mitsui Chemicals, Mitsubishi Chemical, Chiba and others total 863 000 t;
Asia (excluding Japan) MPS (Singapore), FCFC (China Taiwan), Shun Cheong Chemical (China Taiwan), Changchun Petrochemical (China Taiwan), Jin Lake P & B (South Korea), and mainland China together 2.08 million t;
Eastern Europe, Central and South America and other total 562 000 t.
Faced by fast-growing demand for phenol, the world’s major production facilities have been expanded and new equipment introduced. According to statistics, from 2007 to 2009 only in Asia: Japan’s Mitsui Chemicals, Tianjin China Petrochemical, Yanshan Petrochemical, Takahashi petrochemical, Ineos, China Taiwan FCFC, Korea Kumho, LGPC, Thailand PPT, Singapore and MPS, together will add 1.66 million tons of phenol production capacity (of which China will add its 580 000 t) .
2 Technical Development
2.1 phenolic resin
Schenectady International, Inc. established a large-scale phenolic resin plant in Shanghai 2004. The annual production capacity can reach 15 000 t of thermoplastic and thermosetting phenolic resin. Products are mainly used in tire rubber, adhesives, phenolic epoxy molding compounds, abrasive products and casting materials, including octylphenol / formaldehyde resin SP-1068, tall oil modified PF resin SP-6701, cashew shell oil modified resin SP-6700, low free phenol resin HRJ-11995, phenolic curing resin SP-1045,R7530E, a new generation of phenolic adhesive resin Elaztobond TM series, the phenolic resin SSA-27, HRJ1071A for industrial friction material use…
2.2 Phenolic Molding material
New varieties of phenolic molding compounds have high mechanical strength, good heat resistance, leakage resistance, arc resistance and dimensional stability and good performance.
Sumitomo Bakelite developed PM-8280 (general use), PM-8380 (heat resistant) with CTI of 175V, and PM-9250 with CTI of 250V and so on.
The company’s newly developed carbon fiber reinforced phenolic molding compound Vyntec CF8030 with relative density of 1.4, the bending strength of 280MPa, flexural modulus 22GPa, 150 ℃ bending strength of 230MPa, tensile strength of 115MPa, the abrasion resistance: the dynamic friction coefficient of 0.3, Mount consumption rate of 0.02 mm3/min, all these indexes were better than ordinary glass fiber reinforced phenolic molding compound.
To develop high-end market of phenolic molding compounds, Sumitomo Bakelite Company introduced three major products in recent years:
Products PM-8375, PM-9820, PM9630. With the heat resistance, chemical resistance, weather resistance, moisture resistance, to be used in transformer structure, switches and other components;
Products PM-9501, PM-9610 high temperature, dimensional stability, high strength and electrical insulating properties, fit for application of new motor brush holder;
product PM-6630, PM-6432, PM-6830, RX6551S, RX6559S, RX8652S high strength, good heat resistance, small shrinkage, dimensional stability and so on, can to withstand high impact, used in power tools, vacuum cleaners, starter motor commutator fields .
2.3 phenolic resin-based composite materials and curing mechanism
1) Department of Physics, Southern Illinois University launched study on the “nano-porous silica on properties of phenolic resin”. By differential scanning calorimetry, under the temperature at 320 ~ 500K, how porous nano silica pore size (8 ~ 125nm) to influence the curing behavior of the polymer was studied. The results showed that when phenolic resin mixed with nano-porous silica, the curing temperature decreased. However, it is interesting that a linear relationship between the pore size and resin curing temperature, as the smaller the pore size, the higher the curing temperature. The same can be used as arguments to justify that phenolic resin can not penetrate into the pore of the size of 8 nin .
2) Sharif University of Technology Chemical and Petroleum Engineering of Tehran, Iran launched the research on “curing kinetics of polymer-based friction materials ” .
By rheometer study on the curing kinetics of composite friction materials used in railway locomotives had been undertaken. With the friction material and rubber matrix of the curing kinetics, and obtains a mixture of the friction material composition, including the rubber matrix, each of the phenolic resin and the filler cure kinetics of friction materials, and design a model and the phenomenon of Arrhenius-type equation to derive the friction material and rubber matrix curing kinetics and induction time. Model parameters used in different temperature from the flow data, and the most optimal method to calculate the experimental data obtained. Actual measurement data and model good agreement between predicted results, this research also validated the accuracy of the model design. The results show that phenolic resin and fillers on the friction material curing performance of the integrated complex will have a decisive impact. The study by differential scanning calorimetry and other published data proved consistency .
3) Institute of Technology, Polymer Science and Technology, University of Calcutta, India has carried out “bamboo fiber/ Novolac Composites” research. Bamboo fiber reinforced resin composite material is a novolac phenolic resin added with bamboo fiber treated by sodium hydroxidein of different concentrations – and 25% of the other filler. The study also examined the mechanical properties of different composite materials (bending modulus, toughness, tensile strength and elastic modulus).Bamboo fiber after alkali treatment, the physical properties of the composite material, such as wettability has been improved. With the increase of alkali concentration, weight loss of bamboo fiber fraction increased. With silky intensity increased, the mechanical properties also increased. With a quality share of 16% to 20%, bamboo fiber contributed biggest increase in the performance of composite materials. Fourier transform infrared spectroscopy (FFIR) study showed, hydroxyl groups of the bamboo fiber and hydroxymethyl of novolac resin formed aryl ether. When the bamboo fiber content exceeded 20%, the lower the mechanical properties of composite materials, resulting in decrease of the strength of materials of all. Study showed that there is a correlation between composite performance and the interface morphology .
4) The Indian Association of protective materials and storage research and development reserched “reaction parameters effects on particle size of crosslinked spherical phenolic beads by the suspension polymerization of phenol and formaldehyde” .
The crosslinked spherical phenolic beads (PB) were prepared by suspension polymerization of phenol and formaldehyde in alkaline solution. Polyvinyl alcohol (PVA), hexamethylenetetramine (HMTA) and three ethylamine (TEA) was used respectively as stabilizer, crosslinking agent and the basic catalyst. Experiment with different doses of PVA as a stabilizer, in 95 ~ 97 ℃, 550r/min a rotation speed of 4h, generated with high output rate (82.5%) and relatively uniform size (0.2 ~ 1.8mm) of the PB beads. Particle size and distribution can be adjusted by selecting the appropriate medium to the polymerization, including monomer added to the water, changing the relative levels of mechanical agitation and a means to change the stabilizer concentration. PB output rate change with the stabilizer concentration, stirring rate, monomer / water ratio. PB formation and morphology of these factors were described .
5）Hitachi Chemical Co., Advanced Materials R & D Center carried out “using13C-NMR study high-ortho Novolac and Random Novolac the side chain density” .
Using 13C-NMR spectra were investigated through the traditional zinc acetate catalyst and acid catalyst was prepared and high-ortho Novolac random Novolac the side chain density, and using different molecular weight and the ratio of methylene ortho Novolac mark out a phenoxy carbon chemical shifts. Ethane in the dioxane, in the branched chain, straight chain and terminal hydroxyl groups on the phenoxy carbon chemical shifts were 149.2 ~ 151.4,151.4 ~ 153.8,153.8 ~ 156.7, branched chain, straight chain and hydroxyl end groups depends on Novolac share of the mole fraction of molecular weight than the size. However, the high-ortho Novolac and Random Novolac in the side chain density and no difference .
6）The United States AJR Polytron Inc. released important research results on the application of reinforced phenolic molding compound.
They used injection mold to replace the brass and stainless steel materials to reduce costs. In June 2005 NPE Trade Fair held in Chicago, people have seen this “HARd Thred” phenolic enforced by glass fiber. Its potential applications include mobile phones and others widely used in the market.
Thread of Phenolic material by the precision molding has self-locking function. As the glass fiber content is high, it increases torsional stability, so screw is not easy to loose. These plastic inserts tactile than the vertical metal inserts on the rolling flower is much more resilient, making it Niuchu unexpected high intensity. Phenolic insert lighter than the metal inserts, conductivity smaller than in the 204 ℃, good dimensional stability, chemical corrosion resistant and insoluble, and no flow of electrical behavior.
Fair at NPE before an external testing laboratory has proven that the company’s 10-32 silk thread No. 2701201N force units will crack under the peel, while the No. 6-32 screw thread sleeve can withstand the force 145645N. Milton Ross, one in the plastic processing industry who has 50 years of experience in the NPE after that the process can select an improved resin formula, as more external test experiments showed that the new formula allows molding After the size of inserts in the strip before split the load bearing 7003113N continuing to open up a wider range of applications. They will thread wire set of the convex pattern uniform exterior design standards will help make the material in the mold of automated processing easier and help material into the mold cavity. The predicted 75% of sales will be for export. AJR Polytron own production of these inserts in the mold, and it has been used on some products .
Phenolic resin and plastic are widely used, its output is increasing year by year, but their use can not meet the needs of today’s society. Faced by development opportunities, industry consolidation should be strengthened, promoting concentration of production continuously, focus on environmental protection and safety, keep energy saving, producers to increase research investment, to change the structure of phenolic resin, in particular with the other polymer blends, high performance, function, fine, is the main direction of development.Technological innovation of production equipment and molding method will make the phenolic resin and plastics industry dynamic.
Samuel Amanuel．Effects of physical confinement(<125 nm)on the curing behavior of phenolic resin[J]．Journal of Applied Polymer Science，2006，99：3183-3186．
Akbar Shojaei，Care kinetics of a polynler-based composite friction material [J]．Joumal of Applied Polymer Science，2006，100：9-17．
Mahuya DAS．Effects of mercerization of bamboo strips on mechanical properties of unidirectional bamboo-novolac composites[J]．Joumal of Applied Polymer science，2006，100：238-244．
Arjun Singh．Effect of reaction parameters on particle sizes of crosslinked spherical phenolic beads by suspension polymerization of phenol and formaldehyde[J]．Journal of Applied Polymer Science，2006，100：2323-2330．
Masahiro Nomoto．Determination of branch density for high-ortho novolac and random using13 C-NMR[J]．2006(4)：217．
Ineserts．Thermost inserts best brass and stainless[J]．Modem Plasties，2006(11)：57．
Translated by News2phenolic