Study on Preparation of Waterproofing Agent for Mineral Wool Board from Modified C 9 Petroleum Resin

Transcription

1 Petrochemical Research China Petroleum Processing and Petrochemical Technology 2013, Vol. 15, No. 4, pp December 30, 2013 Study on Preparation of Waterproofing Agent for Mineral Wool Board from Modified C 9 Petroleum Resin Li Fengyan; Yang Yajun; Dai Danghui; Yuan Yadong (Department of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing ) Abstract: The modified prepared from the C 9 petroleum resin was modified with maleic anhydride. The effects of maleic rosin and maleic anhydride addition level, the modification time and the alkali liquor on the properties of the emulsion were discussed. The results showed that the optimum process conditions covered: a maleic anhydride mass fraction of 1.5%, a maleic rosin mass fraction of 10%, a KOH mass fraction of 1%, a petroleum resin modification temperature of 200, a petroleum resin modification duration of 3 h, and a modified / wax emulsion mixing ratio of 1:1. The particle size of modified prepared under these conditions was equal to μm. Key words: C 9 petroleum resin, modifier, waterproofing agent, maleic rosin, maleic anhydride 1 Introduction The mineral wool board is a building and ornament material used for sound absorption, fire prevention, decoration and heat insulation. But the mineral wool boards would easily be deformed if they are placed in damp surroundings. So the most critical task in expanding the application of mineral wool board is how to enhance its waterproof performance [1]. The most common waterproofing agent for the mineral wool board is wax. Wang Gaofeng [2] successfully prepared the waterproofing agent by using wax, monoglyceride, peregal and other surfactants as raw materials. Because wax cannot permeate through the mineral wool board easily owing to its non-polar property, so the waterproof performance of the mineral wool is not so good. Although the polar group in the modified petroleum resin can combine well with polar substances in the mineral wool board [3], its waterproof ability is really not so satisfactory. A distinct advantage can be obtained through cleverly combining the wax emulsion and the modified so that paraffin wax and the petroleum resin can be distributed homogeneously across the mineral wool to improve its waterproof ability. With the rapid development of China s petrochemical industry, the capacity of ethylene production units is increasing every year coupled with a surging production of C 9 hydrocarbon fraction. It has been attracting so much attention on how to fully make use of C 9 petroleum resin [4-5]. Owing to the wide variety of C 9 petroleum resin sources and low production cost, in this article the waterproofing agent for the mineral wool board was prepared by means of the modified C 9 petroleum resin. 2 Experimental Materials and instruments: Maleic rosin, C 9 petroleum resin were all technical-grade reagents. Maleic anhydride and KOH were all analytically pure reagents. The instruments used in experiments included a JJ-1 electric mixer (manufactured by the Jintan Medical Instrument Factory), a HH-S water bath (manufactured by the Yuhua Instrument Company), a TGL-16 high-speed centrifuge (manufactured by the Changzhou Guohua Electric Appliance Co., Ltd.), and a LS13320 type laser particle size analyzer (manufactured by the Beckman Coulter Co., Ltd.). Preparation of the modified : (1) The C 9 petroleum resin and the modifying agent were put into the reactor when the reactor temperature was raised to 150. (2) The temperature in reactor was then increased to 200 to transform the mixture into a molten Recieved date: ; Accepted date: Corresponding Author: Professor Li Fengyan, lifengyantd@126.com. 92

2 Li Fengyan, et al. Study on the Preparation of Waterproofing Agent for Mineral Wool Board from Modified C 9 Petroleum Resin state. Then the modified petroleum resin could be obtained after stirring for 3 hours. (3) The maleic rosin was then introduced into the reactor, followed by stirring for 1 hour. (4) The temperature of reactor was reduced to 120 prior to adding a hot alkali liquor containing 10 percent of KOH slowly into the mixture for carrying out the saponification reaction in half an hour. (5) The temperature in the reactor was then decreased to 95 prior to introducing hot water into the reactor for two times separately under stirring for 1 hour and 1.5 hours, respectively. (6) Eventually the C 9 modified can be obtained after filtration. Determination of stability: The emulsion was put in the sample tubes and was then subjected to high-speed centrifugation for 30 minutes at a centrifugal speed of r/min. The ratio of water to oil was recorded to measure the stability of the emulsion. The equation for calculating the ratio of water to oil is shown in Eq. 1: Water/oil ratio= volume of water phase/total volume of emulsion 100% (1) Particle size measurements: The particle size was measured at room temperature by the LS13320 laser particle size analyzer. One or two drops of the modified petroleum resin emulsion were added into the instrument, with the particle size recorded. 3 Results and Discussion 3.1 Effect of the dosage of maleic anhydride The carboxyl group can be introduced into C 9 petroleum resin by addition reaction because the C 9 petroleum resin contains double bonds. The dosage of the maleic anhydride ranged from 1.0% to 2.5% in these experiments. Table 1 shows the properties of product and the phenomena detected during saponification of the modified petroleum resin emulsion which was prepared with different dosage of maleic anhydride. Table 2 shows the result of centrifugation of the waterproofing agent, which was prepared by mixing the modified with the paraffin wax emulsion. The mixing mass ratio between petroleum resin and paraffin was 1:1 and the following experiments were conducted at the same mixing ratio. Table 1 Effect of the dosage of maleic anhydride on the modified Maleic anhydride Reaction proceeded Reaction proceeded Reaction proceeded with Reaction proceeded with Slight precipitation A lot of A lot of Table 2 Effect of the maleic anhydride dosage on the stability of waterproof agent Maleic anhydride % of 1.5 1% of 2.0 Delamination (6%) 2.5 Delamination (13%) It can be seen from Table 1 that the emulsion was not satisfactorily homogeneous due to the existence of larger particles, and the could not proceed smoothly, when the dosage of maleic anhydride was equal to 2.0% or 2.5%. The could proceed when the dosage of maleic anhydride equated to 1.0% or 1.5%. Table 2 shows that the waterproof agent demonstrated no obvious stratification phenomenon and just had a small amount of during centrifugation operation when the dosage of maleic anhydride was 1.0% or 1.5%. However, the stability of the waterproof agent was better when the dosage of maleic anhydride reached 1.5%. The waterproof agent showed no obvious stratification phenomenon when the dosage of maleic anhydride was 2.0% or 2.5%. The stability of the waterproof agent could not be maintained with the increase in the amount of maleic anhydride. The optimum dosage of maleic anhydride was specified at 1.5%. 3.2 Effect of the dispersant The stickiness of the C 9 petroleum resin would be increased when it was heated, and the cohesion could be strengthened. So it was necessary to add some dispersants to make the petroleum resin emulsified easier. The dispersion effect was not so good when less dispersant was 93

3 China Petroleum Processing and Petrochemical Technology 2013,15(4):92-96 introduced. However, not only the resin quality could be affected, but also the thermal stability of the resin would decrease if surplus dispersant was added. The maleic rosin was chosen as the dispersant in this study, and the dosage of maleic rosin ranged from 7.0% to 11.0%. Tables 3 and 4 show the effect of the dosage of maleic rosin on the quality of modified and the stability of the waterproof agent. Table 3 Effect of the dosage of maleic rosin on the modified Maleic rosin with with A lot of Delamination As shown in Table 3, the proceeded with when the dosage of maleic rosin was less than 8.0%, and meanwhile the emulsion was not satisfactorily homogeneous because of the existence of lots of. The could proceed more easily with the increase in the dosage of maleic rosin. But the emulsion would not be satisfactorily homogeneous with the occurrence of lots of again, when the amount of maleic rosin was over 11%. Table 4 Effect of the dosage of maleic rosin on the stability of the waterproof agent Maleic rosin 7.0 Delamination (11%) 8.0 Precipitation (4%) 9.0 Delamination (12%) 10.0 Without delamination and precipitation 11.0 Delamination (19%) As shown in Table 4, there would be delamination when the dosage of the maleic rosin was 7.0%. The delamination phenomenon would trend down with the increase in the dosage of maleic rosin except for the occurrence of a small amount of. The waterproof agent was free from delamination and precipitation phenomena when the dosage of maleic rosin was 10.0%. But the waterproof agent would experience the delamination phenomenon again when the amount of maleic rosin reached 11%. Therefore it can be concluded that the optimum dosage of the maleic rosin should be 10%. 3.3 Effect of the dosage of the alkali liquor The alkali liquor containing 10% of KOH was added to the modified at a ratio of 10 % of the mass of petroleum resin used in this study, and the dosage of KOH could be regulated from 0.5% to 2.0%. Tables 5 and 6 depict the effect of KOH dosage on the quality of modified and the waterproof agent. Table 5 Effect of the dosage of KOH on the modified KOH saponification reaction 0.5 Slight precipitation with with A lot of A lot of Table 6 Effect of the dosage of KOH on the stability of waterproof agent KOH 0.5 Delamination (7.5%) 1.0 Precipitation (1%) 1.5 Delamination (17.5%) 2.0 Delamination (13.5%) As shown in Table 5, the modified had a lot of and the proceeded with when the dosage of KOH was greater than 1.5% or 2.0%. The modified petroleum resin emulsion had less and the saponification reaction could proceed when the dosage of KOH was 0.5% or 1.0%. As shown in Table 6, the waterproof agent had only a small amount of when the dosage of KOH was 1.0%. The waterproof agent would experience the delamination phenomenon when the dosage of KOH was other than 1.0%. 94

4 Li Fengyan, et al. Study on the Preparation of Waterproofing Agent for Mineral Wool Board from Modified C 9 Petroleum Resin Therefore it is concluded that the optimum dosage of KOH was 1.0%. 3.4 Effect of the modification time The effect on modification of petroleum resin was not ideal if the modification time was too short, and on the contrary, it would be a waste of energy if the modification time lasted too long. Tables 7 and 8 show the effect of modification time on the performance of modified petroleum resin emulsion and the stability of the waterproof agent, the modification time ranged from 2 h to 5 h. Table 7 Effect of the modification time on the modified Modification time, h Table 8 Effect of the modification time on the stability of waterproof agent Modification time, h 2 Delamination (16%) 3 Without delamination and precipitation 4 Precipitation (2%) 5 Without delamination and precipitation The modified experienced only slight precipitation and the proceeded when the modification time was between 2 h to 5 h. The waterproof agent did not experience delamination and precipitation, when the modification time was between 3 h to 5 h. The waterproof agent did experience delamination phenomenon when the modification time was 2 h. So the best modification time upon taking into account of energy saving should be 3 hours. 3.5 Effect of the modification temperature The reaction mixture just could not be mixed well when the modification temperature was too low, and without doubt the effect on modification of petroleum resin was unsatisfactory. Moreover, the side reaction would occur easily, if the modification process was carried out at a high temperature. Tables 9 and 10 show the effect of the modification temperature on the quality of modified petroleum resin emulsion and the stability of the waterproof agent. The modification temperature ranged from 160 to 220. Table 9 Effect of the modification temperature on the quality of modified Modification temperature, h with Table 10 Effect of the modification temperature on the stability of waterproof agent Modification temperature, h 220 Precipitation (2%) 200 Free from delamination with a small amount of 180 Precipitation (2%) The modified experienced a slight precipitation phenomenon and the saponification process was easier when the modification temperature was over 180. The waterproof agent did not experience delamination phenomenon albeit with a slight precipitation when the modification temperature was 200. Therefore it was concluded that the optimum temperature of modification was set at Conclusions (a) The optimum process for preparing modified petroleum resin emulsion was implemented at: a maleic anhydride mass fraction of 1.5%, a maleic rosin mass fraction of 10%, a KOH mass fraction of 1.0%, a modification temperature of 200, and a modification reaction time of 3 hours. The average particle diameter of the modified was μm. (b) The waterproofing agent for the mineral wool board could be made by mixing the modified petroleum resin 95

5 China Petroleum Processing and Petrochemical Technology 2013,15(4):92-96 emulsion, which was prepared under optimum conditions, with wax emulsion at a mixing ratio of 1:1. This waterproofing agent featuring high dispersion and high stability did not experience delamination when it was subjected to centrifugation for 30 min at a speed of r/min. (c) Compared with the ordinary paraffin emulsion-based waterproofing agent, the waterproof ability of waterproofing agent prepared with the above-mentioned method was better. If the mineral wool board was used in combination with this waterproofing agent, its moisture resistant grade could reach RH95. References [1] Zhao Fangran. Discussion on the waterproofness and fiber structure characteristics of mineral woolboard[j]. China Building Materials Science & Technology, 2005(6): 40-43(in Chinese) [2] Wang Gaofeng, Huang Qingping, Chen Wenlan. An waterproofing agent for emulsion paraffin used for fiber board: China, CN A[P] [3] Chen Nanxun, Xing Xizeng, Song Xigong. An moisture proof agent for emulsion paraffin used for mineral wool board and its preparation methods: China, CN C[P] [4] Huang Junzuo, Zhang Shisen. Modification technology and application of C 9 petroleum resin[j]. Polymer Bulletin, 2010(4): (in Chinese) [5] Li Chunsheng, Shou Chongqi, Gu Yao. Modification of C9 petroleum resin[j]. Petrochemical Technology, 1999, 28(2): (in Chinese) H-1L Type High Efficiency Slurry Catalyst Secures a Leading International Level The project Commercial application test of TH-1L type high-efficiency slurry catalyst jointly implemented by SINOPEC s Research Institute of Petroleum Processing (RIPP) and Qilu Petrochemical Company (QPC) has passed experts appraisal which was held in Beijing recently. The experts team has unanimously admitted that this catalyst feactures excellent performance and remarkable economic benefits to reach an internationally advanced level. The TH-1L high-efficiency slurry catalyst is a core technology in the field of gas-phase ethylene polymerization process. Currentrly China boasts a total polyethylene production capacity of 10 Mt/a, in which the gas phase ethylene polymerization process accounts for 54.3% of total PE capacity to oocupy a pivotal position. Starting 2005, RIPP and QPC have been engaging in the development of the TH-1L slurry catalyst for polymerization of ethylene. After eight-year-long strenuous efforts in tackling the problem these two institutions have developed the highefficiency slurry catalyst and a novel charging device to secure a commanding lead in this technical area. The TH-1L high-efficiency slurry catalyst has been prepared according to a new preparation process and formulation to enhance its activity, which is about ten times the activity of currently used solid M-1 catalyst. The catalyst preparation process does not use silica gel as the catalyst support to significantly reduce the catalyst cost and simplify the manufacture process flow diagram. Adoption of the novel feeder has allowed for avoidance of online reduction equipment that is required by the overseas catalyst preparation technology. The patents relating to the TH-1L slurry catalyst have been granted by China, the US and other countries. The TH-1L slurry catalyst has been smoothly operating in a 120 kt/a gas phase fluidized bed reactor for 2600 hours at QPC, while successfully cranking out a total of kt of polyethylene resins, including the LDPE film DFDA7042, the MDPE material DNDB7149U, the HDPE extrusion material DGD6084A, and the high transparency PE QLLF30, with all PE granules featuring stable quality and homogeneous size without fine powder. 96