ポリウレタン

ポリウレタンとは　　　日本ポリウレタン工業
http://www.npu.co.jp/whatispur/what_p.html

　ポリウレタン(PU)とはウレタン結合を有するポリマーの総称です。ウレタン結合はイソシアネート基と、水酸基などの活性水素を有する化合物との付加反応により生成されます。

（ウレタン結合、-NH・CO・O-を持つ高分子化合物。ポリエーテルまたはポリエステルとイソシアネート（TDIまたはMDI）を原料として製造される。　石油化学用語辞典）

　イソシアネート基は非常に反応性に富んでいるためこの反応は加熱しなくても進行し、一度反応すると非常に安定な構造をとるという大きな特徴があります。一口にポリウレタンと言ってもその外見は発泡体、フィルム、弾性体、粉末、溶液、エマルジョンなど様々な形を取ります。

イソシアネート基を持つ化合物として、
　　トリレンジイソシアネート　（2,4or2,6-Tolylene diisocyanate）
　　ジフェニルメタンジイソシアネート（4,4'or2,4'-Diphenylmethane diisocyanate）
　　ヘキサメチレンジイソシアネート（1,6-Hexamethylene diisocyanate）
などがあります。　このほかにも、多数のイソシアネート化合物があります。

　水酸基（OH）を２個以上含有する化合物はポリオールとも呼ばれ、一般的には以下の種類のものが使用されています。
　　ポリエーテルポリオール（Polyetherpolyol）
　　ポリエステルポリオール（Polyesterpolyol）
　　ポリカーボネートポリオール（Polycarbonatepolyol）
　　ポリカプロラクトンポリオール（Polycaprolactonepolyol）

　また、水酸基の代わりにカルボン酸、アミン等の活性水素を含有する化合物も併用することができます。このためポリウレタンと言っても無限の種類があるといえるほどです。

この特色を生かし、軟質フォーム、硬質フォーム、エラストマー、接着剤、塗料、バインダーなどの幅広い分野で利用されています。

アデカ

＜ポリエーテルポリオール＞

アデカポリエーテルＰシリーズ
　プロピレングリコールにプロピレンオキサイド（ＰＯ）を付加したポリエーテルジオールです。　
　塗料，接着剤，エラストマー，シーラント用ポリウレタン原料ジオールの他、
　軟質ポリウレタンフォームへの使用も可能です。
　
アデカポリエーテルＢＰＸシリーズ
　ビスフェノールＡにＰＯを付加したポリエーテルジオールです。
　芳香族環を含むため、「アデカポリエーテルＰシリーズ」とは異なった
　耐衝撃性向上、ジイソシアネートとの相溶性良好などの性能を示し、
　塗料，接着剤，エラストマーの他、不飽和ポリエステル樹脂にも適しています。
　
アデカポリエーテルＧシリーズ
　グリセリンにＰＯを付加したポリエーテルトリオールです。
　分子量によって各種ポリウレタンフォームの他、塗料，シーラント用
　ポリウレタン原料としての使用も可能です。
　
アデカポリエーテルＥＤＰシリーズ
　エチレンジアミンの活性水素にＰＯを付加したテトラオールです。
　硬質・半硬質ポリウレタンフォーム用架橋剤の他、
　塗料・接着剤用ポリウレタン原料としても適しています。
　
アデカポリエーテルＳＰ，ＳＣシリーズ
　ソルビトール系及びシュークローズ系にＰＯを付加したポリエーテルポリオールで、
　硬質ポリウレタンフォーム用として適しています。

高反応性ポリエーテルポリオール（アデカポリエーテルＣＭ，ＡＭ，ＥＭ，ＢＭシリーズ）
　ポリエーテルポリオールの末端水酸基にエチレンオキサイドを付加し、
　高反応性化を目指した製品です。
　モールド成形発泡，スプレー発泡の他、エラストマー，塗料，接着剤など
　各用途に応じた製品を揃えています。

アデカポリエーテルＰＲ，ＧＲシリーズ
　ＰＯ，ＥＯランダムポリエーテルで、一級水酸基を多く有する為、反応性が高く、高い親水性も有する。水との相溶性を増大させたポリエーテルポリオールで吸水性，水膨潤性ポリウレタンの原料に適しています。

難燃ポリオール
　「アデカポリエーテルFB-300，FC-450」は末端に水酸基を有する含リンポリオールで、
ポリウレタン用の反応型難燃剤として適しています。
又、硬質ポリウレタンフォーム用メインポリオールとしては、「FL500」が適しています。

ポリマーポリオール
　硬質・半硬質ポリウレタンフォームにおいて、通気性にすぐれ、低密度での硬度が上昇します。

Production Capacity of Polyether Polyols

http://www.ydchem.cn/en/Article_Show.asp?ArticleID=27

　Polyether polyols are main stocks for the production of PU products. Polyether polyols are categorized into three types: the first is a polymer that is formed by polymerization of polyol or organic amine, which act as starting agents, and PO or PO&EO. The polymer is generally termed PPG, this product is needed in the largest quantity for the production of PU. The second is polymeric polyol, which is produced by self-polymerization of ethylene monomers (such as AN or/and SN) and PPG as base materials in the polyol. The polymeric polyol is called POP, POP is not used alone, it is blended with PPG to impart excellent properties to PU products. The third polyether polyol is PTMEG, which is produced by open-ring polymerization of tetrahydrofuran and primarily used in the production of PU elastomers and PU fibers.

　Polyether polyols with different functionality can be produced according to the number of active hydrogen atoms contained in starting agents. Bifunctional polyethers are produced by using binary alcohol ( for example, glycol, propylene alcohol); Trifunctional polyethers are produced by using ternary alcohol ( for example, glycyl alcohol, TMP); Multifunctional polyethers can be produced accordingly by using pentaerythrite (tetratomic alcohol), xylitol (pentatomic alcohol), sorbic alcohol (hexatomic alcohol) and cane sugar (octatomic alcohol).
　
　Production capacity in the world
　
　The production equipments of polyether polyols in the world are relatively large in size, product manufacturing are mainly controlled by several large multinational companies including BASF, Bayer, Dow Chemical Company and Shell Chemical Company. In the year 2005, the production capacity for polyether polyols will total 5,400 thousand tons, and their consumption will also reach over 4,000 thousand tons. In Asia-Pacific territory, the demands for polyether polyols are growing more rapidly than elsewhere across the globe, which will amount to 1,230 thousand tons or so.

　Repsol-YPF company has planned to increase the annual production capacity of epoxy propane equipments by 60 thousand tons in Tarragona, one of its chemical production centers in Spain, the reconstruction project will result in the annual output of 280 thousand tons for epoxy propane in Tarragona. Most of the expanded capacity will contribute to the company’s expansion of polyether polyols, until the year 2005, the production capacity for polyether polyols will increase to 250 thousand tons per year from the present capacity of 200 thousand tons per year. Repsol-YPF company also has epoxy propane/styrene monomers equipments in Puertollano, also one of its chemical production centers in Spain, the center can produce epoxy propane totaling 70 thousand tons a year and polyether polyols 70 thousand tons.

　Shell Netherlands Chemicals Company (SNC) has built a set of new equipments for the production of polymeric polyols in Pernice, Netherlands, the equipments were put into production during the third quarter in 2003, the high quality and high solid content of SAN copolymeric polyols can be produced through the use of the equipments, the output of SAN copolymeric polyols will reach 50 thousand tons per year so as to meet the ever increasing demands from furnishing, mattress and automobile manufacturing. In the coming two years, SNC will continue to invest in building Nanhai Petrolchemicals Joint Company ( a joint venture built jointly by SNC and CNOOC Petrochemicals Investment Corporation), to erect such production equipments as for styrene monomers of annual output 550 thousand tons, for epoxy propane of annual output 250 thousand tons and for polymeric polyols of annual output 185 thousand tons, the above-described equipments are scheduled to be used for production in 2005. Once these projects are completed, SNC will raise its total capacity of producing epoxy propane to 1,130 thousand tons annually, at the same time, the equipments for the production of polymeric polyol of 12 thousand tons a year, which is based on styrene, will stop running.

　The output of PU products in China totaled about 950 thousand tons in 2002, and will total 1,070 thousand tons in 2005. As the PU industry develops rapidly, China’s production capacity of polyether polyol will rise to 280 thousand tons a year by 2005, while the demands will accordingly to 600 thousand tons a year. The main producers and existing production capacities in China are as follows: Tiianjin Petrochemicals No. 3 factory, 60 thousand tons yearly; Gaoqiao Petrochemicals No. 3 factory, 80 thousand tons yearly; Jinling金陵 Petrochemicals Chemical No. 2 Plant, 35 thousand tons yearly; Jinxi 金州Chemical (Group) Corporation, 35 thousand tons yearly (to be expanded to 110 thousand tons a year); Shandong Dongda Chemical (Group) Corporation, 20 thousand tons yearly (to be expanded to 70 thousand tons a year); Jiujiang 九江　Chemical Plant, 20 thousand tons yearly; Zhejiang Pacific Ocean Chemical Company, 40 thousand tons yearly and Shenyang Petrochemicals Plant, 10 thousand tons yearly. The polyehter polyol 330E used in the production of soft foams (abbreviated 330E polyether) accounts for two thirds of the total output of polyether, the annual output of 330E polyether is 70 thousand tons, the demands for it in the domestic market is 160 thousand tons per year, the annual insufficiency of supplies is 80 thousand tons.

　The production capacity of polyether polyol within JIN HUA 金華　GROUP has reached 110 thousand tons a year, and (epoxy propane 125 thousand tons a year). More than 40 brands of polyether polyols are available for many applications. Shanghai Gaoqiao Petrochemicals No. 3 Factory had a production capacity of polyether polyol as much as 85 thousand tons in 2001, and as much as 120 thousand tons in 2002 by adding five production lines. In Shandong Dongda Chemical Group, after its reconstruction for expanding its production capacity, the output of polyether polyol reached 70 thousand tons in 2001 (including POP 10 tons produced by the continuous process). In December 2002, the equipments for the production of polyether polyol with 20 thousand tons a year were put into use within Tianjin Dagu Chemical Company, they proved a success. In 2003, the Bay of Meizhou in Fujian Province witnessed a polyether polyol factory having 20 thousand tons a year put into production. The production in the recent two years, some private companies specializing in annually 10 thousand tons-sized polyether polyol for hard foams have been set up in Jiangsu Province, Zhejiang Province, Shandong Province and Hebei Province. Up to 2002, the production capacity of polyether polyol has amounted to 400 thousand tons a year in China. The polyether polyol project having annual output of 185 thousand tons invested jointly by Guangdong Huizhou and SNC has been launched. It is estimated that the production of polyether polyol soon be self-governed and saturated in Chinese PU industry. Also, many business giants have entered the Chinese market through the acquisition of Chinese enterprises, and made direct investments in the polyether polyol manufacturing of China, this has brought fresh pressure in relevant industries in China.

　Polymeric polyol (abbreviated POP) is a class of graft modification polyether polyol, which is new-type feed stock in the production of PU foam, and has properties to improve the bearing capacity and foam cell-opening ability of PU foam. It is the non-deformation of POP that makes POP suitable for the production of foam, it is essential feed stock in manufacturing top grade mattress, cushions, etc.. Shanghai Gaoqiao Petrochemicals Company has developed successfully a polymeric polyol-GPOP-H30. GPOP-H30 is a kind of highly active and high solid content polymeric polyol, it is synthesized from the materials primarily including highly active polyether, styrene, AN, macromolecular monomer, polymerization controller and initiator, etc. Shanghai Gaoqiao Petrochemicals No. 3 Factory (a subordinated enterprise of Shanghai Gaoqiao Petrochemicals Company) has erected polymeric polyol equipments having the production capacity of 15 thousand tons a year, this will be favorable in improving quality of foam extensively, and raise the output of polymeric polyol by 25% in China. The amount of 25,650 thousand RMB was invested in this project, it is projected that the invested amount will be returned in three years and a half. The project has the advantage of paying particular attention to environmental-friendly production, the disposal of waste gas, water and industrial residual is subject to special means. In 2002, Nantong Xinyuan Foam Company built a polymeric polyol continuous production line which has the annual production capacity of over 10 thousand tons, the main products are XY-02/43 and XY-02/46, which have the high solid content, can be blended with normal polyether in a varying mixing ratio, or be used alone. The products XY-02/43 and XY-02/46 can improve the hardness of foam, they are suitable for the production of soft cube ?foams and cold mould foams, their various qualifications have approached the quality level of its kind that is imported from foreign countries. Polymeric polyol equipments having 10 thousand tons capacity will be put into production in Tianjin Dagu Chemical Company in July 2003.

　In recent years, in terms of R&D of polyether polyol, the most representative breakthrough is low degree of unsaturation polyether polyol. In recent ten years, many foreign producers have pushed their low degree of unsaturation polyether polyol on the market, for example, Axxlaim series from Atlantic Richfield Company, Poly-L series from Olin company, HP series from BASF company and CARADOL series from SNC, these products seem to almost overwhelm the Chinese market. Low degree of unsaturation polyether polyol is the most representative breakthrough in the production of PU, its core technology is the application of bimetallic catalysts, the technology is characterized by a small amount of catalysts and the absence of after treatment when polyether with relative molecular weight below 4000 is produced. This technology is good for reducing cost and environmental friendly. This core technology has opened vast vistas in its applications of sealants, coatings, adhesive agents and high resilience foams. Jinling Petrochemicals Research Institute successfully developed a low degree of unsaturation polyether polyol?DMC in 1998, and in 2000, the trial production process was a success. Compared to the existing alkaline catalysts that are used to produce polyether polyol products, highly active bimetallic catalysts feature better catalytic activity, higher reactivity and more stable quality. In July 2003, low degree of unsaturation polyether polyol industrial trial project implemented jointly by Jinling Petrolchemical No. 2 Factory, Jinling Petrochemical Research Institute and Shanghai Gaoqiao Petrochemicals Company was verified by China Petroleum & Chemical Corporation (Sinopec Corp.), in this project, it is the first time within China that low degree of unsaturation polyether polyol is successfully applied to the industrial production of 10 thousand tons output polyether, the product yield reached 99.5%. Since 2001, some large polyether ?producing enterprises such as Shanghai Gaoqiao Petrochemicals No. 3 Factory and Jinling Petrolchemical No. 2 Factory have employed bimetallic complex compound catalysts in industrial equipments to produce low degree of unsaturation polyether for supplying the market. The resulting polyether catalyzed by using this series of catalysts are stable in quality, PU also have excellent properties.

　Low degree of unsaturation polyether polyol produced by Tianjin Petrolchemical No. 3 Factory and Jinling Petrolchemical No. 2 Factory, etc. has been initially commercialized.

　Highly active and low degree of unsaturation polyether polyol developed by Liming Chemical Research Institute and ω-amino polyether developed by Jiangsu Province Chemical Research Institute have been put into industrial trials.

　Other new products also include a high solid content POP manufactured by JIN HUA GROUP and Tianjin Petrochemical No. 3 Factory, POP having an annual capacity of 10 thousand tons produced by a continuous process and vegetable polyether polyol (used for the production of hard foams) in Shandong Dongda Chemical Group.

　Among the consumption of polyether polyol in China during 1997-2001, 75% is used to produce elastic foam materials (soft foams), most of the rest is used to produce hard foams. Although the consumption of hard foams is much lower than that of soft foams, its applications are expanding rapidly, its consumption has risen from 130 thousand tons in the year 1997 to 160 thousand tons in this year. About 56% of hard foams’ consumption finds its applications in the ice refrigerator and icehouse industries, whereas 25% in the construction industry. However, 49% of polyether polyol is used in the construction industry in the developed countries, while 43% used in this industry in Japan. In China, polyether polyol has strong market potential in the construction industry, so have the products that are used for the production of CASE (coatings, adhesive agents, sealants and elastomers), their market shares are growing rapidly in recent years. With the development of the automobile industry in China, polyether polyol have found rapidly increasing demands from PU automobile parts, for instance, in the Chinese-made car (CA7220), the weight of PU parts accounts for 0.83% of the car’s total weight.

　CPUIA analyzed the supply-demand relations of polyether polyol in Asia-Pacific Territory during the period of 1997-2005, and concluded that the domestic production capacity is far from meeting the market demands for polyether polyol. The polyether polyol industry of China is being challenged by fresh developing opportunities, in the past ten years, an industrial foundation has been laid, the market demands look to further increase. Whereas the domestic demands exceed supplies, the major world producers are seeking the business opportunities to develop their production and sales of polyether polyol, quite a few multinational companies specializing in producing PU materials have proposed to invest in building several sets of large polyether polyol equipments, Bayer PU (Shanghai) subsidiary company will build a set of polyether polyol equipments with the capacity of 280 thousand tons a year in Shanghai Chemical Industry Zone. The polyether polyol project having annual output of 185 thousand tons within Nanhai Petrolchemicals Joint Company invested jointly by CNOOC and SNC has been launched, this will soon change the current production situations in China. The polyether polyol used in the PU industry in China will become self-sufficient and saturated. After China joins WTO, the existing import quota system will be gradually cancelled, the domestic polyether polyol producers will face stern challenges, therefore, it is an extremely urgent thing to make their competitive force far stronger.