• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Synthesis and Application of Polyurethane Modified Organic Silicone Wet Rubbing Fastness Improver

    2015-12-20 09:13:24TONGDongfeng仝東鳳LIUXueDONGChaohong董朝紅LIUJie

    TONG Dong-feng (仝東鳳),LIU Xue (劉 學(xué)),2* ,DONG Chao-hong (董朝紅)* ,LIU Jie (劉 杰)

    1 College of Chemical and Environmental Engineering,Qingdao University,Qingdao 266071,China

    2 Key Laboratory of Special Textile Processing Technology of Shandong Province,Qingdao 266032,China

    Introduction

    Reactive dyes contain groups that react with the hydroxyl(OH)groups in cellulose.Reactive dyes for protein fibers and nylon have also been offered by dye manufactures,but dyeing of cellulose is the major use for dyes in the reactive classification.However,the dyes suffer the disadvantage that dye fiber reaction is not 100% efficient[1].The reaction between the dye and the fiber is a nucleophilic displacement.Since the by-product of the reaction is an acid and because alkali increases the negative nature of the oxygen atom on cellulose,the above reactions are catalyzed by alkali.Dye molecules,which react with the fiber and become fixed,have excellent fastness to washing because of the high strength of the covalent bonds.But dye molecules,which are hydrolyzed may be weakly attached to the fiber and if not washed out at the end of the dye cycle,have very poor washfastness.Especially when the fabric is dyed to a deep color,a great amounts of dye molecules that cannot react with fiber gather together on the surface of the fibers,which results in a very poor wet rubbing fastness of reactive dyes[2].Several kinds of color fastness improver agents have been reported on the application in improving the wet rubbing fastness of dyed fabrics,however,the hand feeling of the treated fabric would be influenced greatly[3-4].Therefore,a multi-functional agent which can improve both color fastness of dyed fabrics and fabric handle feeling should be developed.

    Polyurethanes have been gaining importance in a wide range of applications such as foam materials,water proof materials,paints,and adhesives because of their good physical and mechanical properties.And it is easy to control the surface properties,such as toughness,flexibility,adhesion on substrate,and anti-abrasion resistance[5-7].Aqueous polyurethane could form 3D mesh film on the surface of fiber and encapsulate dyes,by which the dyes were protected from hydrolyzing.Furthermore,aqueous polyurethane could react with reactive groups of dyes and fibers,by which the wet rubbing fastness of dyed cotton fabric could be effectively improved[3].The application of silicone softeners turns hard and rough fabric into a soft pleasant textile with which the buyer can expect a high degree of wearing comfort.Silicone have wide spread application in the textile industry from fiber,yarn and fabric production to final product finishing[8].The friction between fibers is decreased significantly due to organic silicone molecules attached onto fiber,thus the softness of fabric is improved.In order to combine the valuable properties of the two polymers, cross-linking structure of organic siliconepolyurethane systems were often designed[9].For these reasons,the experiment employed hydroxyl-terminated polyethermodified silicone,and toluene-2,4-diisocyanate (TDI)as raw materials,and synthesized polyurethane-modified silicone with sodium bisulfate capped.The chemical structure of the polyurethane modified organic silicone was also investigated.In addition,the application properties of the polyurethane modified organic silicone were also studied.

    1 Materials and Methods

    1.1 Materials

    Hydroxyl-terminated polyether modified silicone,TDI,NaHSO3,Drimaren Red K-2G,Drimaren Yellow K-6G,Drimaren Blue K-GR (these dyes were provided by Clariant)were applied in this study.The hydroxyl-terminated polyether modified silicone used in this study were dried at 100 ℃ in vacuum for 4 -5 h in advance to remove all air bubbles and water vapors.All of the reagents used in this study were analytical grade.

    1.2 Synthesis of the polyurethane modified organic silicone

    First of all,hydroxyl-terminated polyether modified silicone(Fig.1)was charged into a four-necked round bottom flask equipped with a mechanical stirrer,a thermometer,a reflux condenser,heating oil bath,and a nitrogen gas inlet system.The temperature of the oil bath was increased to a certain temperature.Then some TDI were added to the reaction vessel.It took some time to obtain NCO terminated.The NCO contents of polymer were determined and found close to the theoretical value.At last,the temperature of the reaction vessel was decreased to certain temperature and some NaHSO3were introduced into the reaction mixture.It took some time to form yellow transparent liquid in the reaction vessel which was the indication of the formation of polyurethane modified organic silicone (Fig.2).

    1.3 Dyeing process

    The pre-wetted fabrics by distilled water were dyed in a dye bath with liquor ratio 50 ∶1.The dyeing process employed is shown in Fig.3.After being dyed,the dyed sample was rinsed thoroughly in cold water and then hot water.At last,the dyed sample was rinsed in cold water and allowed to dry in the open air.

    Fig.1 Hydroxyl-terminated polyether modified silicone

    Fig.2 Polyurethane modified organic silione

    Fig.3 Dyeing process

    1.4 Treatment of cotton fabrics with the polymer

    The cotton fabrics were immersed in a solution of the polyurethane modified organic silicone at 30 ℃for 5 min.The wet fabrics were squeezed using a laboratory mangle with a pick-up 65%.The fabrics were then dried at 85 ℃for 3 min and cured at 160 ℃for 90 s with a preheated laboratory tenter to fix polyurethane modified organic silicone on the cotton fabrics.

    1.5 Characterization of the polymer

    The polyurethane modified organic silicone was determined by FT-IR spectra and1H-NMR.

    Physical parameters such as solid contents (%),emulsion stability, emulsion appearance, and PH value of the polyurethane modified organic silicone were shown.

    Emulsion stability was evaluated by storage time.The emulsion state remains the same under the certain storage time.

    1.6 Characterization of cotton fabric with the polyurethane modified organic silicone

    The surface morphology of the fabric was determined by scanning electron microscopy (SEM).

    The chemical groups present on cotton surfaces were analyzed by FT-IR.

    The XRD patternswere determined by powder X-ray diffraction measurements.

    1.7 Testing methods

    The wet rubbing fastness properties of the fabrics dyed with different dyes such as Red K-2G,Blue K-GR,and Yellow K-6G were tested through GB/T3920—1997 standard methods.

    The softness was evaluated by hands feel method,which needed at least three people subjective assessment.

    2 Results and Discussion

    2.1 Molecular structural characterization

    Figure 4 (a)showed the FT-IR spectrum of the polyether modified organic silicone.The bands at 2 900 and 3 475 cm-1were assigned to C—H and O—H bonds which appeared on polyether modified silicone.The strong absorption at 1 250 cm-1was due to Si—CH[10].The bands in a range of 1 150-1 100 cm-1were due to C—O—C and Si—O—Si[10-13].The peak at 835 cm-1was assigned to Si—CH3bond[13-14].Figure 4(b)showed the FT-IR spectrum of the polyurethane modified organic silicone.The peak at 835 cm-1was assigned to Si—CH3rocking[13-14].The band at 3 475 cm-1assigned to O—H stretching disappeared.There were no absorption peaks at 3 475 cm-1,which indicated that no O—H bond existed in the polyurethane modified organic silicone the monomers were polymerized.There was the peak at 1 725 cm-1=of C O of ester and 1 530 cm-1was attributed to N—H bond vibration and C—N symmetry stretch vibration[12,14].The band at 2 270 cm-1was NCO characteristic absorption peak.So the carbamate had been generated.These showed that the polyurethane modified organic silicone had been modified successfully.

    1H-NMR is the most useful for the measurement of hydrogen chemical environment because of its high sensitivity to hydrogen bond strength,while the area of apex also evidently reflects the abundance of hydrogen in different chemical shift.[8]Figure 5 showed the1H-NMR spectrum of the polyurethane modified organic silicone.Observed peaks at 0.029-0.066 mg/L were attributed to methyl groups of the organic silicone segment structure.Methylene groups of polyether segment appeared at 3.552-3.647 mg/L.A peak at 7.26 mg/L was assigned to C—H bond of benzene ring in TDI.Small peak appearing at 2.16 mg/L was attributed to methyl groups of benzene ring in TDI.Also weak peak appearing at 2.017 mg/L was due to N—H bond of carbamate.

    Fig.4 FT-IR spectra of (a)the polyurethane modified organic silicone and (b)the polyether modified silicone

    Fig.5 1H-NMR spectrum of the polyurethane modified organic silicone

    2.2 Physical characterization

    In this work,the polyurethane modified organic silicone emulsion of different dosage of NCO was prepared.Table 1 showed physical parameters such as solid contents (%),emulsion stability,emulsion appearance and pH value of the polyurethane modified organic silicone.These characteristics are important and helpful for the further application of the emulsions.It could be seen that pH value was 6-7.Emulsion appearance was almost the same in all studied samples.Solid content of the synthesized material was in the range of 20%-30%.And the solid content of the polyurethane modified organic silicone decreased with the increase of different NCO contents.The reason of this phenomenon may be that the increase of NCO contents contribute to form cross-linking.So the viscosity of polyurethane modified silicone has increased.It clearly indicated that emulsion stability of No.5 was only 1 week.Over time, a part of the emulsion gelled.The phenomenon may be due to the free isocyanate groups that can crosslink with each other in the emulsion.

    Table 1 Physical characterization of the polyurethane modified organic silicone

    2.3 SEM images of the polymer

    Figure 6 showed the SEM analyses of surface changes of cotton fabric with the polyurethane modified organic silicone.Figure 6 (a)showed the rough surface of cotton fabric.There were many tiny grooves.When SEM images in Figs.6 (a)and(b)were compared,it was clear that the cotton fiber of Fig.6(b)were covered with the polyurethane modified organic.Because of the higher film-form ability of polyurethane,it could form a layer of protective film on the surface of fiber.It was considered that the polyurethane modified organic silicone had been attached to the fiber surface.Figure 6 (c)showed the cotton fabric with the polyurethane modified organic silicon treatment after 20 times washing.It was found that the film on the surface of fabrics were damaged to a certain extent,but it still existed on the fiber surface.The reason of the phenomenon may be that polyurethane modified organic silicone finishing agent end capped with sodium bisulfite released NCO at a certain temperature.Then the covalent cross-linking structures could be formed between NCO and OH of cellulose fibers.

    Fig.6 SEM of (a)cotton fabric,(b)cotton fabric with polyurethane modified organic silicone treatment,and (c)cotton fabric with the polyurethane modified organic silicon treatment after being washed 20 times

    2.4 FT-IR spectra of cotton fabric studies

    Figure 7 showed the FT-IR spectra of untreated cotton and fabric with the polyurethane modified organic silicone.Figure 7 (b)showed the FT-IR spectra of cotton fabric with the polyurethane modified organic silicone treatment compared with the untreated cotton shown in Fig.7 (a).The band at 3 450 cm-1was assigned to O—H bonds,which normally appeared on cotton surface,had lower intensity than the untreated surface.This was because the covalent cross-linking structures could be formed between NCO and OH of cellulose fibers.The band at 2 900 cm-1assigned to C—H stretching had higher intensity than the untreated surface due to Si—CH3groups.The absorption at 1 725 cm-1=reflected C O stretching of ester group in polyurethane modified organic.The peak at 1 530 cm-1was attributed to N—H bond vibration and C—N symmetry stretch vibration.The absorption at 1 250 cm-1was due to Si—CH.The peak at 850 cm-1was assigned to Si—CH3rocking.From these analyses,it was clear that polyurethane modified organic silicone had reacted with cellulose fibers.

    Fig.7 FT-IR spectra of (a)cotton fabric and (b)cotton fabric with polyurethane modified organic silicone treatment

    2.5 XRD of cotton fabric studies

    Figure 8 showed the XRD of cotton fabrics of untreated or treated with the polyurethane modified organic silicone.It was found that there were the same strong diffraction peaks at 14.8°,16.7°,22.8°,and 34.3°.It was indicated that the crystalline regions of cotton fibers did not change after finishing.So the main reaction between cotton and polyurethane modified organic silicone occurred in the amorphous areas and the surface of cotton fibers.

    2.6 Effect of fabric wet rubbing fastness

    Table 2 showed the effect of fabric wet rubbing fastness treated with polyurethane modified organic silicone.There have been reports that polyurethane modified organic silicone containing reactive groups (NCO)could react with reactive groups of dyes and fibers,thus reducing dye hydrolysis.Therefore,the rubbing fastness of deep color cotton fabrics was improved effectively.The rubbing fastness properties of cotton fabric before and after finishing were shown in Table 2.It was revealed that all the wet rubbing fastness was above rating 3.Meanwhile,all the dry rubbing fastness has been improved.And the wet rubbing fastness of different reactive dyed fabric had got enhanced in different degrees.It was not selective for reactive dyes.Wet rubbing fastness of fabric dyed with three kinds of reactive dyes was significantly improved after being treated with the polyurethane modified organic silicone.The organic silicone molecules adsorbed onto the fiber greatly decreased the friction between fibers,thus the softness of cotton fabrics was improved.As can be seen from Table 2,the softness of the cotton fabrics was improved from rating 1 to rating 5.

    Fig.8 XRD of (a)cotton fabric and (b)cotton fabric with polyurethane modified organic silicone treatment

    Table 2 Rubbing fastness properties of cotton fabric after finishing

    2.7 Color aberration after finishing

    Table 3 showed color aberration of the samples after the treatment with polyurethane modified organic silicone.The DL(depth of color)and Dc(vidiness of color)values of the samples decreased after treatment with polyurethane modified organic silicone,the shade becoming darker.This is due to lower refractive index of silicone agent solutions,which reflect less light,thus the silicone agent treated samples show a darker shade[15].The Da(the color of red to green component),Db(the color of yellow to blue component),and Dcvalues of the treated samples changed after treatment.The color of finished fabrics became blue-green.The reason may be that the combination of the polyurethane modified silicone with dye molecules affected the molecular structure of the dye conjugated system.There was little change of DE(the total color difference)for the polyurethane modified organic silicone.

    Table 3 Color aberration after finishing

    2.8 Performance comparison

    Table 4 showed the performance comparison results of fabrics treated with different finishing agent.It was observed that the fabrics treated with polyurethane modified organic silicone had the same softness compared with the fabrics treated by organic silicone softeners.However,there was a remarkable increase in rubbing fastness of treated fabrics by polyurethane modified organic silicone compared with the samples treated by organic silicone.This was because the reactive groups (NCO)of polyurethane modified organic silicone reacted with reactive groups of dyes and fibers.The polyurethane segment of polyurethane modified organic silicone formed 3D mesh film on the surface of fibers and protected the dyes from hydrolyzing.This implies that polyurethane helps to improve the rubbing fastness of the treated fabrics.

    Table 4 Performance comparison of different finishing agent

    3 Conclusions

    (1)The chemical structure of the polyurethane modified organic silicone was characterized by FT-IR and1H-NMR.It was confirmed that the polyurethane modified silicone polymers were successfully synthesized using TDI and hydroxylterminated polyethers modified organic silicone as raw materials.

    (2) The polymer film on the cotton surface was investigated by SEM and the results showed that a thin polymer film was successfully formed.The FT-IR of treated cotton fabrics indicated that the covalent cross-linking system had been formed between OH of cellulose fibers and NCO of the polyurethane modified organic silicone.The polyurethane modified organic silicone finishing agent end capped with sodium bisulfite has released NCO at a certain temperature.XRD analyses revealed that the crystalline region of treated cotton fabrics wasn't changed after finishing,implying the main reaction of cotton and polyurethane modified organic silicone occurred in the amorphous areas of cotton fibers.

    (3) Polyurethane modified organic silicone polymer emulsion is a very good wet rubbing fastness agent,which can improve the wet rubbing fastness of the fabric dyed by reactive dyes by rating 1.There was little change of DE values for the polyurethane modified organic silicone.In addition,the softness of treated cotton fabrics was excellent.

    [1]Burkinshaw S M,Katsarelias D.A Study of the Wash-off and Aftertreatment of Dichlorotriazinyi Reactive Dyes on Cotton[J].Dyes and Pigments,1995,29(2):139-153.

    [2]Zheng Q S,Li L,Wang W,et al.Study on Parameters of Saving Protease for Cashmere Shrink Proof[J].Journal of Xi'an Polytechnic University,2010 (3):279-284.(in Chinese)

    [3]Xu J,Zhu Q.Application Process of Improver WPU for Wet Rubbing Fastness[J].Dyeing and Finishing,2006(24):17-19.(in Chinese)

    [4]Mao Z P,Lu Q M,Qin D H,et al.The Effect of the Wet Rubbing Fastness Improver ZQ-W on the Properties the Fabrics Dyed with Reactive Dyes[J].Textile Auxiliaries,2005,22(4):20-21.(in Chinese)

    [5]Daemia H,Rad R R,Barikani M,et al.Catalytic Activity of Aqueous Cationic Polyurethane Dispersions:a Novel Feature of Polyurethanes[J].Applied Catalysis A:General,2013,468:10-17.

    [6]Ge Z,Luo Y J.Synthesis and Characterization of Siloxane-Modified Two-Component Waterborne Polyurethane [J].Progress in Organic Coatings,2013,76(11):1522-1526.

    [7]Castagna A M,F(xiàn)ragiadakis D,Lee H K,et al.The Role of Hard Segment Content on the Molecular Dynamics of Poly(tetramethylene oxide)-Based Polyurethane Copolymers [J].Macromolecules,2011,44(19):7831-7836.

    [8]Naghash H J,Abili B.Synthesis of a Silicone Containing Allylic Monomer and Its Uses in the Waterborne Polyurethane/Vinyl Acetate-Acrylic Hybrid Emulsion Copolymers[J].Progress in Organic Coatings,2010,69(4):486-494.

    [9]Zubera M,Zia K M,Tabassum S,et al.Preparation of Rich Handles Soft Cellulosic Fabric Using Amino Silicone Based Softener,Part II:Colorfastness Properties [J].International Journal of Biological Macromolecules,2011,49(1):1-6.

    [10]Akovali G,Rzaev Z M O,Mamedov D G.Plasma Surface Modification of Polyethylene with Organosilicon and Organotin Monomers[J].European Polymer journal.1996,32(3):375-383.

    [11]Jia X,Li Y F,Cheng Q,et al.Preparation and Properties of Poly (vinyl alcohol)/Silica Nanocomposites Derived from Copolymerization of Vinyl Silica Nanoparticles and Vinyl Acetate[J].European Polymer Journal,2007,43(4):1123-1131.

    [12]Tang E J,Cheng G X,Shang Q,et al.A Novel Approach to the Preparation of Powder Coating-Manufacture of Polyacrylate Powder Coatings via One Step Minisuspension Polymerization[J].Progress in Organic Coatings,2006,57(3):282-287.

    [13]Teshima K,Sugimura H,Inoue Y,et al.Wettability of Poly(ethylene terephthalate)Substrates Modified by a Two-Step Plasma Process:Ultra Water Repellent Surface Fabrication[J].Chemical Vapor Deposition,2006,10(6):295-297.

    [14]Parvinzadeh M.The Effects of Softeners on the Properties of Sulfur-Dyed Cotton Fibers [J].Journal of Surfactants and Detergents,2007,10(4):219-223.

    [15]Daemi H,Barikani M,Barmar M.Compatible Compositions Based on Aqueous Polyurethane Dispersions and Sodium Alginate[J].Carbohydrate Polymers,2013,92(1):490-496.

    日本免费在线观看一区| 一本—道久久a久久精品蜜桃钙片| 国产人伦9x9x在线观看 | 大话2 男鬼变身卡| 精品一区二区三区四区五区乱码 | 九草在线视频观看| 国产黄色免费在线视频| 国产精品欧美亚洲77777| 1024视频免费在线观看| 最新中文字幕久久久久| 久久青草综合色| 97精品久久久久久久久久精品| 亚洲精品一区蜜桃| 国产男女超爽视频在线观看| 欧美精品一区二区免费开放| 在线观看美女被高潮喷水网站| 亚洲国产色片| 午夜福利乱码中文字幕| 男女啪啪激烈高潮av片| 久久ye,这里只有精品| 色婷婷久久久亚洲欧美| 欧美av亚洲av综合av国产av | 超色免费av| 中文字幕色久视频| 日本欧美国产在线视频| 久久精品熟女亚洲av麻豆精品| 99精国产麻豆久久婷婷| 各种免费的搞黄视频| 亚洲精品av麻豆狂野| 青春草国产在线视频| 日韩电影二区| 欧美精品人与动牲交sv欧美| 欧美中文综合在线视频| 侵犯人妻中文字幕一二三四区| 国产精品久久久av美女十八| 边亲边吃奶的免费视频| 大片电影免费在线观看免费| 亚洲 欧美一区二区三区| 久久久精品94久久精品| 大香蕉久久网| 午夜福利在线观看免费完整高清在| 欧美激情极品国产一区二区三区| 97在线视频观看| 精品亚洲成a人片在线观看| 日韩在线高清观看一区二区三区| 黑丝袜美女国产一区| 午夜av观看不卡| 99久久中文字幕三级久久日本| 亚洲内射少妇av| 久久久久久久久免费视频了| 一区二区三区乱码不卡18| 免费黄色在线免费观看| 国产免费又黄又爽又色| 99精国产麻豆久久婷婷| 精品国产一区二区久久| 午夜激情久久久久久久| 久久99精品国语久久久| 99香蕉大伊视频| 国产成人精品婷婷| 欧美日韩国产mv在线观看视频| 亚洲欧美精品综合一区二区三区 | 成年人午夜在线观看视频| 女人被躁到高潮嗷嗷叫费观| 久久狼人影院| 欧美激情 高清一区二区三区| 香蕉丝袜av| 成人手机av| 免费久久久久久久精品成人欧美视频| 热re99久久国产66热| 在现免费观看毛片| 老司机影院成人| 免费黄色在线免费观看| 午夜福利视频在线观看免费| 亚洲人成网站在线观看播放| 日本免费在线观看一区| 成人手机av| 日韩制服骚丝袜av| 校园人妻丝袜中文字幕| 一二三四在线观看免费中文在| av在线老鸭窝| 女人久久www免费人成看片| 香蕉国产在线看| 美女主播在线视频| 黑人猛操日本美女一级片| av卡一久久| 2021少妇久久久久久久久久久| 夜夜骑夜夜射夜夜干| 啦啦啦视频在线资源免费观看| 人人澡人人妻人| 男女国产视频网站| 久久97久久精品| 黑人猛操日本美女一级片| 久久综合国产亚洲精品| 亚洲精品久久午夜乱码| 久久久精品94久久精品| 女人精品久久久久毛片| 精品久久蜜臀av无| 在线观看三级黄色| 免费观看无遮挡的男女| 久久青草综合色| 又黄又粗又硬又大视频| 秋霞伦理黄片| 久久人妻熟女aⅴ| 色吧在线观看| 国产精品久久久久久av不卡| 久久久久久久国产电影| 欧美+日韩+精品| 天天操日日干夜夜撸| 日本色播在线视频| 精品一区在线观看国产| 久久久久久久久免费视频了| 人妻人人澡人人爽人人| 伊人久久国产一区二区| 男人添女人高潮全过程视频| www.av在线官网国产| av免费观看日本| 有码 亚洲区| 国产精品久久久久久av不卡| 黑人巨大精品欧美一区二区蜜桃| 日本黄色日本黄色录像| 如日韩欧美国产精品一区二区三区| 中文精品一卡2卡3卡4更新| 午夜福利视频精品| 国产精品久久久久久精品电影小说| 秋霞伦理黄片| 免费观看av网站的网址| 久久久久久伊人网av| 一区二区三区四区激情视频| 亚洲国产欧美日韩在线播放| 久久久久精品人妻al黑| 如日韩欧美国产精品一区二区三区| 久久97久久精品| 国产亚洲一区二区精品| 亚洲久久久国产精品| 日韩人妻精品一区2区三区| 成人国语在线视频| 免费在线观看视频国产中文字幕亚洲 | 精品第一国产精品| 免费看av在线观看网站| 亚洲成av片中文字幕在线观看 | 高清黄色对白视频在线免费看| 少妇人妻久久综合中文| 高清不卡的av网站| 国产日韩欧美在线精品| 成人毛片60女人毛片免费| 99热网站在线观看| 一区二区三区乱码不卡18| 久久久久久人妻| 亚洲男人天堂网一区| 亚洲av日韩在线播放| 99香蕉大伊视频| 亚洲国产精品一区三区| 国产片特级美女逼逼视频| 国产爽快片一区二区三区| 亚洲国产精品999| 永久免费av网站大全| 成人国产av品久久久| 丝袜人妻中文字幕| 激情五月婷婷亚洲| 国产日韩欧美视频二区| 亚洲久久久国产精品| 午夜福利,免费看| 国产欧美日韩综合在线一区二区| 女性被躁到高潮视频| 国产黄色视频一区二区在线观看| 亚洲久久久国产精品| 永久网站在线| 天堂8中文在线网| 国产成人aa在线观看| 尾随美女入室| 日本av免费视频播放| 亚洲精品乱久久久久久| 久久久久久免费高清国产稀缺| 国产精品不卡视频一区二区| 午夜av观看不卡| 国产综合精华液| 亚洲五月色婷婷综合| 在线观看人妻少妇| 国产成人精品福利久久| 日韩中字成人| 国产人伦9x9x在线观看 | 午夜精品国产一区二区电影| 久久精品国产亚洲av高清一级| 色吧在线观看| 久久精品国产综合久久久| 亚洲国产欧美日韩在线播放| 亚洲第一区二区三区不卡| 少妇的丰满在线观看| 精品久久久精品久久久| 国产日韩欧美亚洲二区| 欧美日韩综合久久久久久| 少妇人妻 视频| 伦理电影免费视频| 国产精品免费视频内射| 考比视频在线观看| 亚洲av国产av综合av卡| 久久热在线av| 韩国av在线不卡| 国产一区二区三区综合在线观看| 亚洲欧洲国产日韩| 在线观看美女被高潮喷水网站| 亚洲精品成人av观看孕妇| 另类亚洲欧美激情| 汤姆久久久久久久影院中文字幕| 99久久精品国产国产毛片| 97在线人人人人妻| 天天躁夜夜躁狠狠久久av| 中文精品一卡2卡3卡4更新| 国产精品三级大全| 国产一级毛片在线| 免费大片黄手机在线观看| 在线观看免费日韩欧美大片| 综合色丁香网| 久久久久国产精品人妻一区二区| 亚洲经典国产精华液单| 性少妇av在线| 精品卡一卡二卡四卡免费| 国产乱人偷精品视频| 国产乱人偷精品视频| 亚洲图色成人| 中文字幕最新亚洲高清| 国产精品免费大片| 久久久久国产一级毛片高清牌| 国产高清不卡午夜福利| 国产av精品麻豆| 欧美最新免费一区二区三区| 黄片小视频在线播放| 久久久精品免费免费高清| 熟女av电影| 99精国产麻豆久久婷婷| 母亲3免费完整高清在线观看 | 五月天丁香电影| 卡戴珊不雅视频在线播放| 在线 av 中文字幕| 不卡av一区二区三区| 秋霞在线观看毛片| 精品少妇一区二区三区视频日本电影 | av女优亚洲男人天堂| 狂野欧美激情性bbbbbb| 成人二区视频| 亚洲av在线观看美女高潮| 宅男免费午夜| 天天操日日干夜夜撸| 97在线视频观看| 热re99久久精品国产66热6| 中文字幕人妻丝袜一区二区 | 欧美日韩成人在线一区二区| 国产av国产精品国产| www.自偷自拍.com| 免费女性裸体啪啪无遮挡网站| 成人国产av品久久久| 国产老妇伦熟女老妇高清| 水蜜桃什么品种好| 精品国产一区二区三区四区第35| 午夜福利,免费看| 一区二区日韩欧美中文字幕| 国产成人精品在线电影| 久久99精品国语久久久| 国产极品粉嫩免费观看在线| 国产成人精品婷婷| 欧美国产精品一级二级三级| 曰老女人黄片| 18禁观看日本| 亚洲精品一二三| 久久精品亚洲av国产电影网| 日韩免费高清中文字幕av| 美女中出高潮动态图| 亚洲欧美一区二区三区黑人 | 国产精品久久久久久精品古装| 国产免费又黄又爽又色| av免费在线看不卡| 9热在线视频观看99| 欧美精品一区二区免费开放| 国产精品免费视频内射| 欧美精品一区二区大全| 一二三四中文在线观看免费高清| 久久精品国产亚洲av天美| 国产精品香港三级国产av潘金莲 | 99热网站在线观看| 亚洲国产av影院在线观看| 久久女婷五月综合色啪小说| 狠狠婷婷综合久久久久久88av| 美女大奶头黄色视频| 国产黄色免费在线视频| 午夜av观看不卡| 免费观看a级毛片全部| 日韩伦理黄色片| av网站在线播放免费| 一级毛片我不卡| 一个人免费看片子| 国产精品成人在线| 亚洲,一卡二卡三卡| 久久人人爽人人片av| 精品少妇黑人巨大在线播放| 亚洲av成人精品一二三区| 国产在视频线精品| 国产淫语在线视频| 国产精品一国产av| 色婷婷久久久亚洲欧美| 老司机影院毛片| 中文精品一卡2卡3卡4更新| 在线观看www视频免费| 岛国毛片在线播放| 少妇的丰满在线观看| 国产精品99久久99久久久不卡 | 欧美日本中文国产一区发布| 美女xxoo啪啪120秒动态图| 精品99又大又爽又粗少妇毛片| 国产av精品麻豆| 欧美国产精品一级二级三级| 中文字幕制服av| 日本免费在线观看一区| 中文字幕人妻熟女乱码| 欧美人与性动交α欧美软件| 热99久久久久精品小说推荐| 菩萨蛮人人尽说江南好唐韦庄| 一本大道久久a久久精品| 久久毛片免费看一区二区三区| 最新的欧美精品一区二区| av电影中文网址| 80岁老熟妇乱子伦牲交| 亚洲色图 男人天堂 中文字幕| 99九九在线精品视频| 国产淫语在线视频| 18在线观看网站| 国产av国产精品国产| 欧美激情 高清一区二区三区| 精品久久久久久电影网| 老司机影院成人| 国产毛片在线视频| 中国三级夫妇交换| 亚洲少妇的诱惑av| 18在线观看网站| 久久精品久久精品一区二区三区| 国产一区有黄有色的免费视频| av在线观看视频网站免费| 伦理电影免费视频| 国产成人午夜福利电影在线观看| 国产精品无大码| 成人影院久久| 精品人妻一区二区三区麻豆| 成人手机av| 韩国av在线不卡| 久久精品人人爽人人爽视色| av一本久久久久| 久久久久久人妻| 天堂中文最新版在线下载| 极品人妻少妇av视频| 飞空精品影院首页| 寂寞人妻少妇视频99o| 久久午夜综合久久蜜桃| 久久久a久久爽久久v久久| 91午夜精品亚洲一区二区三区| 日本av手机在线免费观看| 久久亚洲国产成人精品v| 国产一区二区在线观看av| 在线免费观看不下载黄p国产| 成人免费观看视频高清| 男女高潮啪啪啪动态图| 99久久人妻综合| 日韩一本色道免费dvd| 久久午夜综合久久蜜桃| 免费在线观看完整版高清| 日本wwww免费看| 亚洲欧美中文字幕日韩二区| 成人亚洲精品一区在线观看| 制服人妻中文乱码| 熟妇人妻不卡中文字幕| 久久免费观看电影| 好男人视频免费观看在线| 午夜福利一区二区在线看| 亚洲欧洲国产日韩| 久久精品久久久久久久性| 2022亚洲国产成人精品| 午夜福利影视在线免费观看| 久久久久精品人妻al黑| 一边亲一边摸免费视频| 国产无遮挡羞羞视频在线观看| 亚洲久久久国产精品| 久久影院123| 一级爰片在线观看| 91aial.com中文字幕在线观看| 又黄又粗又硬又大视频| 女性生殖器流出的白浆| 多毛熟女@视频| 欧美亚洲日本最大视频资源| 26uuu在线亚洲综合色| 曰老女人黄片| 欧美激情极品国产一区二区三区| 亚洲欧洲日产国产| 狠狠精品人妻久久久久久综合| 天堂中文最新版在线下载| 免费观看性生交大片5| 在线观看一区二区三区激情| 午夜av观看不卡| 欧美人与性动交α欧美软件| 新久久久久国产一级毛片| av视频免费观看在线观看| 久久精品久久久久久噜噜老黄| 少妇 在线观看| 亚洲欧美色中文字幕在线| 最新的欧美精品一区二区| 99久久精品国产国产毛片| 不卡视频在线观看欧美| 国产男女内射视频| 丝瓜视频免费看黄片| 午夜福利在线观看免费完整高清在| 七月丁香在线播放| 久久精品国产亚洲av天美| 大香蕉久久成人网| 777久久人妻少妇嫩草av网站| 久久久国产精品麻豆| av一本久久久久| 男人舔女人的私密视频| 国产成人免费观看mmmm| 亚洲精品中文字幕在线视频| av网站在线播放免费| 成年av动漫网址| 亚洲精品日韩在线中文字幕| 黄片播放在线免费| 国产无遮挡羞羞视频在线观看| 在线精品无人区一区二区三| 叶爱在线成人免费视频播放| 日本wwww免费看| xxxhd国产人妻xxx| 久久国内精品自在自线图片| 少妇精品久久久久久久| 丝袜美腿诱惑在线| 国产成人91sexporn| 一本大道久久a久久精品| 国产乱人偷精品视频| 精品国产露脸久久av麻豆| av网站在线播放免费| 国产老妇伦熟女老妇高清| 美女高潮到喷水免费观看| 国产熟女午夜一区二区三区| 美女国产高潮福利片在线看| 精品一品国产午夜福利视频| 亚洲一区二区三区欧美精品| 日韩 亚洲 欧美在线| 午夜福利在线免费观看网站| 黄色毛片三级朝国网站| 色94色欧美一区二区| 久久综合国产亚洲精品| 不卡视频在线观看欧美| 久久午夜综合久久蜜桃| 亚洲国产日韩一区二区| 观看美女的网站| 亚洲国产日韩一区二区| 我的亚洲天堂| 在线精品无人区一区二区三| 男人爽女人下面视频在线观看| 国产成人精品福利久久| 在线观看美女被高潮喷水网站| 久久久久久久大尺度免费视频| 久久人妻熟女aⅴ| 啦啦啦中文免费视频观看日本| 18禁国产床啪视频网站| 亚洲熟女精品中文字幕| 最近中文字幕高清免费大全6| 男人添女人高潮全过程视频| 日韩大片免费观看网站| 在线免费观看不下载黄p国产| 一区二区三区精品91| 下体分泌物呈黄色| 香蕉丝袜av| 卡戴珊不雅视频在线播放| 久久亚洲国产成人精品v| 国产高清国产精品国产三级| 日韩精品免费视频一区二区三区| 七月丁香在线播放| 伊人久久国产一区二区| 国产精品成人在线| 欧美成人午夜精品| 人成视频在线观看免费观看| 午夜91福利影院| 国产伦理片在线播放av一区| 日日爽夜夜爽网站| 亚洲国产精品999| 男女高潮啪啪啪动态图| 日韩视频在线欧美| 桃花免费在线播放| 美女午夜性视频免费| 国产一区二区在线观看av| 国产精品久久久久久久久免| 亚洲av国产av综合av卡| a级毛片黄视频| 丝袜人妻中文字幕| 老司机影院成人| 熟女电影av网| 精品少妇内射三级| 女人久久www免费人成看片| 91久久精品国产一区二区三区| 国产日韩欧美在线精品| 久久这里只有精品19| 在线亚洲精品国产二区图片欧美| 看非洲黑人一级黄片| 少妇熟女欧美另类| 欧美bdsm另类| 成人二区视频| 欧美日韩成人在线一区二区| 天堂俺去俺来也www色官网| 成人国产麻豆网| 飞空精品影院首页| 欧美日韩视频精品一区| 热re99久久精品国产66热6| 亚洲一区二区三区欧美精品| 亚洲欧美一区二区三区久久| 欧美精品一区二区大全| av女优亚洲男人天堂| 天堂中文最新版在线下载| 中文字幕精品免费在线观看视频| 国产av精品麻豆| 国产成人aa在线观看| 天天躁夜夜躁狠狠久久av| 国产精品久久久久成人av| 亚洲成人av在线免费| 欧美日韩精品网址| 国产成人精品无人区| 亚洲精品国产av成人精品| 女性生殖器流出的白浆| 91在线精品国自产拍蜜月| 一本一本久久a久久精品综合妖精 国产伦在线观看视频一区 | av电影中文网址| 亚洲精品视频女| 最近的中文字幕免费完整| 欧美精品一区二区大全| 国产精品99久久99久久久不卡 | 亚洲av国产av综合av卡| 久久精品夜色国产| 久久99一区二区三区| 久热久热在线精品观看| 一区在线观看完整版| 国产成人欧美| 五月伊人婷婷丁香| 精品国产超薄肉色丝袜足j| 最近最新中文字幕免费大全7| videos熟女内射| 亚洲国产av影院在线观看| 精品人妻一区二区三区麻豆| 日韩一卡2卡3卡4卡2021年| 亚洲精华国产精华液的使用体验| 9色porny在线观看| 亚洲,欧美,日韩| 久久久久久久久免费视频了| 黄频高清免费视频| 男人爽女人下面视频在线观看| 伊人亚洲综合成人网| 老司机影院成人| 欧美在线黄色| 99国产综合亚洲精品| √禁漫天堂资源中文www| 亚洲欧美成人精品一区二区| 黄片播放在线免费| 中文字幕人妻丝袜一区二区 | 在线观看免费高清a一片| 欧美激情极品国产一区二区三区| av卡一久久| 色94色欧美一区二区| 精品少妇一区二区三区视频日本电影 | 9色porny在线观看| 99re6热这里在线精品视频| 黑人巨大精品欧美一区二区蜜桃| 国产黄频视频在线观看| 侵犯人妻中文字幕一二三四区| 国产成人精品久久久久久| 午夜免费鲁丝| 精品视频人人做人人爽| 男人操女人黄网站| 高清欧美精品videossex| 日本黄色日本黄色录像| 久久精品久久精品一区二区三区| 日本黄色日本黄色录像| 久久国产亚洲av麻豆专区| 亚洲国产成人一精品久久久| 久久久精品国产亚洲av高清涩受| 免费黄频网站在线观看国产| 叶爱在线成人免费视频播放| 久久 成人 亚洲| 黑丝袜美女国产一区| av卡一久久| av视频免费观看在线观看| 天天躁日日躁夜夜躁夜夜| 男女免费视频国产| 男人爽女人下面视频在线观看| 少妇的逼水好多| 黑人猛操日本美女一级片| 午夜福利,免费看| 国产成人免费无遮挡视频| 丝袜美腿诱惑在线| 免费不卡的大黄色大毛片视频在线观看| 亚洲av在线观看美女高潮| 少妇人妻 视频| 久久久久久免费高清国产稀缺| 大片电影免费在线观看免费| 亚洲国产精品999| 一二三四中文在线观看免费高清| 久久久久久久国产电影| 午夜日本视频在线| 日日摸夜夜添夜夜爱| 国产有黄有色有爽视频| 夫妻午夜视频| 熟女电影av网| 我要看黄色一级片免费的| 视频在线观看一区二区三区| 国产精品国产三级国产专区5o| 黄频高清免费视频| 亚洲四区av| 亚洲一区二区三区欧美精品| 国产无遮挡羞羞视频在线观看| 99热国产这里只有精品6| 熟女av电影| 热re99久久国产66热| 欧美激情高清一区二区三区 | 男的添女的下面高潮视频|