Adhesion of cornstarch-g-poly (2-hydroxyethyl acrylate) to cotton fibers in sizing

Abstract

A range of starch-g-poly (2-hydroxyethyl acrylate) (S-g-PHEA) with different grafting ratio was prepared by graft copolymerization of 2-hydroxyethyl acrylate (HEA) onto granular cornstarch using ammonium cerium nitrate as initiator. The adhesive ability of the sizes to cotton fibers, film properties, and desizing ability of HEA branch grafted onto starch were investigated. The effects of grafting conditions (such as reaction time, temperature, HEA and initiator concentration, etc.) on grafting ratio and efficiency were investigated. Fourier transformed infrared spectroscopy (FTIR) and Thermogravimetric analysis (TGA) was employed to characterize the complexes of S-g-PHEA. The effect of grafting ratio on the sizing properties of grafted starch was studied by testing the ability of the grafted starch to adhere to cotton fiber and film properties. It was confirmed that the HEA branch can effectively improve the adhesion ability of starch to cotton fibers, improves the flexibility of the starch film while reduces the brittleness, and enhances the abrasion resistance of the yarns (the highest enhancement ratio up to 225.71%). An increase in the grafting ratio facilitates the adhesion to the cotton fibers while making the desizing difficult. The desizing efficiency was high when the grafting ratio was less than 10%, which lead to easy access to desizing and then fewer residues have remained, and at the same time, good sizing performance is maintained, which indicates that the S-g-PHEA possesses the application potential of cotton warp sizing.     

固相法淀粉接枝甲基丙烯酸甲酯共聚物的制备与表征

以过硫酸铵为引发剂,在少量水存在下,研究了玉米淀粉（CS）与甲基丙烯酸甲酯（MMA）接枝共聚的反应规律。考察了含水量、反应时间与温度、MMA单体和引发剂用量等因素对接枝共聚反应的影响。实验结果表明,体系含水质量百分数为40％左右、MMA用量为CS质量的15％、过硫酸铵用量为CS质量的8％、反应温度在80℃、反应时间为0．5h左右,可得到接枝率和接枝效率均较高的接枝共聚物。通过红外光谱（FTIR）、热重分析法（TGA）以及X射线衍射法（XRD）对合成的接枝共聚物进行了表征。     

接枝-氧化-酯化淀粉浆料的制备

以H2O2／NaHSO3为引发剂,水为分散介质,玉米淀粉与醋酸乙烯酯接枝聚合后再经氧化酯交换反应制备了淀粉浆料．经IR光谱确认了接枝共聚物。研究了工艺条件对接枝参数的影响,确定了较佳的制备工艺：ω（H2O2／NaHSO3）=1：3．引发剂为0．40％,接枝反应温度为35℃,接枝反应时间为2h。此浆料80％替代PVA用于T／C80／2013．1×13．1433×299160经纱上浆,织机效率高达90％．具有很好的经济效益和环境效益。     

Synthesis and Characterization of Starch-Poly(vinyl Acetate) Graft Copolymers and their Saponified Form

A redox initiation system based on potassium persulfate/acetone sodium bisulphite (KPS/ASBS) was developed to initiate the graft copolymerization of vinyl acetate (VAc) monomer onto corn starch in aqueous solution. The grafting reaction was studied with respect to grafting yield (GY), grafting efficiency (GE) and total conversion (TC) and results obtained were compared with those a well-established redox initiation system namely potassium persulfate/sodium bisulphite (KPS/SBS). The effect of reaction variables such as redox initiator concentration, liquor ratio, reaction time and temperature as well as VAc concentration were investigated. The GY, GE and TC increased significantly with increase of the redox initiation concentration up to 8/16 mmol/l irrespective of the initiation system used. Moreover, optimal grafting was obtained at 60 ^○C for KPS/ASBS redox system and 70 ^○C for KPS/SBS redox system. Saponification of poly (vinyl acetate)-starch graft copolymers were effected using NaOH in three different bath media (n-hexane, acetone or methanol) to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). Higher extent of solubility in hot water of the saponified form was achieved by using a bath containing n-hexane/sodium hydroxide; however, increasing the graft yield higher than 26.3% decreases the solubility. The structures and thermal stability of starch, grafted starch copolymer and saponified grafted starch copolymer were characterized by infrared spectroscopy and thermogravimetric analysis. Moreover, the rheological behavior as well as sizing performance of the saponified grafted starch copolymers were evaluated and compared with the native starch and commercial polyvinyl alcohol.     

Characterization of cationic polyacrylamide‐grafted starch flocculant synthesized by one‐step reaction

Cationic polyacrylamide‐grafted starch (St‐g‐CPAM) flocculant was prepared by using corn starch and acrylamide (AM) as monomers, dimethyl diallyl ammonium chloride (DMDAAC) as cationic monomer through solution polymerization. The effects of initiator, reaction temperature, and monomer concentration on flocculation, the efficiency of grafting, and the yield of grafting were investigated. The results show that the optimal conditions of the polymerization are as follows: the concentration of ceric ammonium nitrate is 0.5%, the reaction temperature is 60°C, the concentration of total monomer is 20%, and the monomer ratio between AM and DMDAAC is 7 : 3. The flocculation capability was characterized by turbidity reduction. The thermal behavior, chemical structure, and microstructure of St‐g‐CPAM were also investigated by thermal gravimetric, IR, and SEM analyses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microwave irradiated synthesis of grafted cationic starch: Synthesis,characterization, application,and biodegradation

A biodegradable copolymer was synthesized by grafting copolymerization of acrylamide, β‐hydroxyethyl methacrylate, and n‐butyl acrylate onto corn cationic starch (CS) by microwave irradiation. The grafted cationic starch (GCS) was characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, and X‐ray diffraction. The optimum conditions on graft copolymerization with respect to reaction temperature, exposure time, and initiator concentration were investigated. Physicochemical properties of GCS, such as swelling power, solubility, intrinsic viscosity, and apparent viscosity, were studied, and its application performances as textile sizing agent were tested. Results showed that compared with CS, physicochemical properties of GCS were significantly improved, including decreased crystallinity, weakened granular, increased hydration capacity, and rheological property. Polyester/cotton blended yarns sized with GCS obtained more reinforced mechanical properties than samples sized with CS and exhibited higher tensile strength and abrasion resistance than polyvinyl alcohol (PVA) sized yarns. The mechanisms that the starch physicochemical properties affected on the sizing performances were discussed as well. Biodegradation analysis on these sizing agents showed that BOD₅/COD_cr of GCS was 0.263, which outclasses that of PVA (BOD₅/COD_cr = 0.009). This novel biomaterial could be expected to have promising applications especially in textile industry and be an ideal substitute for PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1645–1652, 2013     

丙烯酰胺改性玉米淀粉/PVA复合膜的制备与表征

为了改善聚乙烯醇（PVA）膜的机械性能,选用玉米淀粉为原材料,50℃条件下以过硫酸铵和尿素为引发剂,同时加入丙烯酰胺对淀粉进行接枝改性,制备得到丙烯酰胺改性的玉米淀粉/PVA复合膜。其中,优化改性淀粉的接枝率确定最佳合成条件为淀粉/丙烯酰胺的质量比为3∶7、引发剂过硫酸铵占单体总质量的0.5%、尿素占单体总质量的0.5%。进一步利用优化的改性淀粉为改性剂,制备了系列改性玉米淀粉/PVA复合膜。采用傅里叶红外光谱、扫描电子显微镜（SEM）对复合膜的组成与结构进行表征,同时测定复合膜的机械性能、耐水性、耐热性等物化特性,结果表明30%ST-0.50%APSU改性淀粉的单体转化率为95.0%,接枝率为85.2%。 30%ST-0.50%APSU/PVA复合膜的耐热性能轻微下降,但断裂伸长率提高了256%,耐水性能提高了43.1%。     

紫外光辐射接枝及胺化法制备温敏性聚乙烯薄膜

实验探索在水性体系中经紫外光辐射,引发丙烯酸(AAC)在聚乙烯(PE)薄膜表面接枝,并经过胺化反应,在已改性的丙烯酸-聚乙烯(AAC-g-PE)薄膜上继续引入功能团,使改性后的PE薄膜具有温度敏感性。考察了引发剂用量、紫外光照射时间对接枝率的影响,并对不同胺化剂合成产物的温敏效应进行比较,从而达到实验目的。通过红外光谱和尺寸变化率证明丙烯酸接枝在PE表面,胺化反应后,生成聚N-异丙基丙烯酰胺聚合聚乙烯(PNIAAm-g-PE)薄膜和聚N-正丙基丙烯酰胺聚乙烯(NNPA-g-PE)薄膜具有温敏性。     

Optimization of synthesis and characterization of cassava starch‐graft‐poly(acrylonitrile) using response surface methodology

Graft copolymerization of poly(acrylonitrile) onto cassava starch was carried out with potassium persulphate (PPS) as the free radical initiator using a response surface Box–Behnken design. Different levels of monomer concentration, initiator concentration, and temperature were used, and regression models were generated in terms of these factors, which can be used to predict the grafting level and efficiency at a given level of the factors. The grafted starches were characterized by FTIR, XRD, and SEM analyses and determination of %grafting (%G), N‐content, thermal properties, water and saline solution retention, and rheological properties. Under the conditions used, %G was found to depend only on the temperature used for the reaction. The maximum %G of 120.1 was obtained for the sample synthesized under the following conditions: weight of AN = 0.753 mol/10 g starch, weight of PPS = 0.284 g and temperature = 55°C, and the grafting efficiency was 30.03%. The absorption bands at 2243 cm^?1 for the nitrile group (? CN) in the FTIR spectra of the products confirmed the grafting reaction. There was a decrease in crystallinity and disappearance of the granular structure after grafting of the starch. The melting temperatures of the graft copolymers determined by differential scanning calorimetry analysis were higher than that of the native starch. The grafted starches exhibited very high thermal stability as observed from the thermogravimetric analysis. The superabsorbent polymer prepared from the grafted starch by alkali saponification exhibited a maximum water absorbency of 636 g/g. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

淀粉-MMA接枝共聚物的半干法合成新工艺

以硝酸铈铵(CAN)为引发剂,采用固相半干法合成了玉米淀粉(CS)接枝甲基丙烯酸甲酯(MMA)共聚物。考察了含水量、反应体系的酸性、反应时间与温度、MMA单体和引发剂CAN用量等因素对接枝共聚反应的影响。结果表明,体系含水质量分数为35%左右,CAN用量为CS质量的1.5%～3%,反应温度在40～50℃,反应时间为0.5h左右,可得到接枝率、接枝效率和单体转化率均较高的接枝共聚物。     

双氧水引发下淀粉／丙烯腈接枝聚合物的制备与分析

以淀粉为原料,在双氧水的引发下,与丙烯腈进行接枝反应制备淀粉接枝聚合物。考察了温度、时间、引发剂浓度、接枝剂浓度等单因素对接枝率的影响。对影响接枝反应的各种因素,如反应物的用量、反应时间、引发剂浓度等进行了深入细致的分析探讨,由正交试验确定出双氧水为引发剂,进行淀粉接枝反应的最佳工艺条件为：反应温度85℃,反应时间3h,料液比1：100,引发剂浓度17．143mmoL／L,丙烯腈浓度0．114mmol／L。     

Synthesis and physicochemical properties of graft copolymer of corn starch and acrylamide

Graft copolymerization of corn starch with acrylamide using ceric ammonium sulphate/citric acid initiation system has been studied under nitrogen atmosphere in aqueous medium. The grafting parameters are favored by increasing monomer concentration and reaction time but are affected by higher concentration of initiator and high temperature. The optimum conditions established for grafting were as follows: the concentration of initiator, 0.003 mol/L; the concentration of citric acid, 0.03 mol/L; monomer/starch, 1:1 feed ratio (w/w); reaction time, 3.0 h; and temperature, 35°C. The extent of grafting was examined by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Both swelling power and solubility increased with the increase in temperature. Graft copolymerization increased swelling power and reduced solubility. Rapid visco‐analyzer pasting profile was studied. Graft copolymerization of corn starch results in high pasting temperature, high peak viscosity, and setback as compared with native starch. Breakdown was retarded at low percentage grafting (6.60%) but increased at high percentage grafting (60.27%). POLYM. COMPOS. 28:47–56, 2007. © 2007 Society of Plastics Engineers     

CAN - KPS体系引发淀粉接枝共聚为絮凝剂的工艺研究

为克服引发剂铈盐较昂贵,工业应用难的缺点,实验采用CAN-KPS复合引发体系引发丙烯腈接枝改性淀粉,采用接枝率和接枝效率作为评价接枝效果的指标,详细研究了接枝工艺及其引发剂浓度、丙烯腈单体的用量和接枝温度对接枝率和接枝效率的影响,结果表明:接枝率达130%以上,接枝效率达90%以上,可较好地代替铈盐引发剂。接枝后对接枝淀粉的结构分析表明:淀粉大分子上已接枝上丙烯腈单体;接枝反应不仅发生在淀粉的无定形区也发生在结晶区,且接枝后接枝淀粉的结晶度有所提高。     

甲基丙烯酸羟乙酯接枝改性淀粉的制备及性能

甲基丙烯酸羟乙酯(HEMA)与降解淀粉(ST)在过硫酸铵(APS)引发下,通过接枝共聚反应,制备了接枝改性淀粉,讨论了APS、HEMA、反应温度和反应时间对接枝效率(GE)和接枝率(GP)的影响。结果表明,在w(ST)=16.4%的水溶液中,当w(HEMA)=5.08%,w(APS)=0.84%时,于50℃反应280 min后,所得接枝改性淀粉的GE和GP分别为40%和27.5%。红外光谱(FTIR)和凝胶渗透色谱(GPC)确证了产物结构。复鞣革应用结果表明,接枝改性淀粉复鞣革的增厚率、丰满度、柔软性、弹性、发泡感等有所提升。接枝改性淀粉复鞣革的力学性能与参考样相当,产物具有复鞣性能。     

Effect of amphoteric grafting branch on the adhesion of starch to textile fibers

Starch-g-poly(2-methacryloyloxyethyl trimethyl ammonium chloride-co-acrylic acid) (starch-g-P(DMC/AA)) with different zeta potentials was prepared via the graft copolymerization of acid-thinned cornstarch (ATS) with 2-methacryloyloxyethyl trimethyl ammonium chloride (DMC) and acrylic acid (AA) in aqueous medium using Fe²⁺–H₂O₂ initiator. The investigation was carried out to reveal the influence of amphoteric branches grafted onto starch chains upon the adhesion of starch to textile fibers. Zeta potential of starch-g-P(DMC/AA) was adjusted by altering the mole ratio of DMC to AA charged into the copolymerization system. The adhesion was evaluated in terms of bonding strength and specific bonding strength of slightly sized roving based on a legal method (FZ/T 15001-2008) through the comparison of the amphoteric branch-grafted starch with ATS, starch-g-PAA, and starch-g-PDMC for warp sizing. It was found that the charged branches grafted onto starch chains were able to significantly enhance the adhesion. Zeta potential, depending on the mole ratio of DMC to AA units in the grafting branches, showed evident effect on the adhesion and desizability of the grafted starch. Increase in the potential favored to improve the adhesion, but disfavored the removal of the starch from sized warps. Alkali-oxidant agent desizing test confirmed that the starch-g-P(DMC/AA) with neutral potential was desizable. The amphoteric branch-grafted starch exhibited potential application as size base materials in warp sizing operation if its zeta potential was neutral.     

Synthesis and characterization of graft copolymers of ethyl acrylate/acrylamide mixtures onto starch

Graft copolymerization of ethyl acrylate/acrylamide onto corn starch using potassium permanganate–citric acid initiation system was investigated. Major factors affecting the polymerization reaction were thoroughly investigated in terms of initiator concentration, monomer concentration, polymerization time, polymerization temperature, and starch/liquor, and the obtained results implied that the polymer yield which were expressed by total monomer conversion, grafting ratio, and grafting efficiency were determined by these factors. The optimum reaction conditions were as follows: starch, 30 g; potassium permanganate (based on weight of starch), 0.1%; citric acid (based on weight of starch), 0.5%; ethyl acrylate, 20%; acrylamide, 0.4 g; time, 3 h; temperature, 40°C; starch/liquor, 1:3. We concluded that the initiator of potassium permanganate–citric acid system could be used as a cheap initiator in manufacturing the starch graft copolymer. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

涂料用玉米淀粉-苯乙烯接枝共聚乳液的制备与性能

以过硫酸钾为引发剂,在乳化剂OP存在下,玉米淀粉与苯乙烯接枝聚合制备了涂料用淀粉-苯乙烯乳液,经红外光谱确认了共聚物。研究了工艺条件对乳液聚合的影响,确定了较佳的乳液制备工艺:玉米淀粉于85℃糊化酸降解1 h,加入聚乙烯醇和乳化剂,按m(苯乙烯)∶m(淀粉)∶m(过硫酸钾)=20∶8∶0.28,在80~85℃接枝共聚3 h。引发剂分3个阶段加入:苯乙烯单体加入前先加入引发剂质量的20%,然后在2 h内均匀加入全部单体和引发剂质量的60%,最后加入剩余的20%引发剂反应1 h。以此乳液为成膜物质复配成的乳胶涂料的性能达到或超过GB/T9756—2001合格产品的指标:耐水性≥96 h,耐洗刷性≥500次,耐碱性24 h无异常。     

纸厂回收淀粉用于纸张施胶剂的制备与应用

以纸厂回收并经过处理的废淀粉作为聚合物的主链,通过接枝苯乙烯(St)、丙烯酸丁酯(BA)及甲基丙烯酸甲酯(MMA)等单体,合成出一种稳定的苯丙乳液施胶剂。结果表明:当w(引发剂)=2.5%~4%、反应温度为70~80℃和m(总单体)∶m(废淀粉)=1∶1.5时,废淀粉接枝共聚物乳液施胶剂的综合性能最好;该施胶剂能有效提高原纸张的各项性能,在同等条件下其性能略低于市售施胶剂;废淀粉回收价格较低,将其用于纸张施胶剂的制备,可达到降低污染、节约成本等目的。     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

以丙烯腈改性淀粉为分散剂的阳离子苯丙乳液的研制

以丙烯腈改性淀粉为分散剂,采用自由基聚合法在淀粉分子链上接枝苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酸二甲基氨基乙酯(DM)和丙烯酰胺(AM)等共聚单体,合成出一种新型的阳离子型淀粉接枝苯丙乳液施胶剂。探讨了K2S2O8/NaHSO3氧化还原型引发剂、共聚单体等对施胶剂施胶效果的影响。结果表明:当w(DM)=2%、w(AM)=0.3%、m(改性淀粉)∶m(单体)=1.0∶1.5、m(St)∶m(BA)=2.3∶1.0、引发剂中m(K2S2O8)∶m(NaHSO3)=1.0∶1.0且氧化剂w(K2S2O8)=0.10%时,施胶剂的施胶效果最佳,并且优于传统苯丙乳液施胶剂。