Study On The Synthesis And Performance Of Tall Oil Based Fatliquor

The paper industry is developing rapidly in recent years,so a large number of paper-making black liquor is produced.After further washing,the upper layer of black liquor is crude tall oil.Currently,most of the tall oil?TO?is exported or treated as a kind of low-end raw material,only a small amount was transferred to fatty acids,tall oil rosin and other products.The economic benefits are extremely low.How to make full use of tall oil to produce quality products has become an important domestic R & D direction.In this study,tall oil?TO?is modified by sulfation,sulfitation and phosphorylation,and then they are used in leather fatliquoring process to improve the leather's handle and performances,which can not only increase the value of TO,but also expand application scope.Firstly,TO and concentrated sulfuric acid were as raw materials to synthesize sulfated tall oil.After being neutralized with ammonia water,sulfated tall oil fatliquor?S-TO?was prepared.The structures of S-TO were characterized.The optimum reaction conditions were as follows: reaction time was 6 h,reaction temperature was 40?,molar ratio of concentrated sulfuric acid to tall oil was 1:5,the rotation speed was 600 r/min.The emulsification time of S-TO prepared under the best reaction conditions was the longest.At the same time,the HLB value of the emulsion was 12.4,the particle size was 81.2nm,as well as the emulsion had good resistance to chromium salt,resistance to tannin extract and alkali stability,but poor acid stability.The structure and properties of the leather before and after being fatliquored by S-TO and commercially available fatliquor S-NO were characterized.The results showed that the leather thickening rate was increased.The water vapor permeability of fatliquors was reduced.The tensile strength and tear strength of leather fatliquored by S-TO were increased and the increase effect was similar to S-NO.SEM results showed that the collagen fiber become more loose.The comprehensive fatliquoring effect indicated that S-TO can achieve a commercial fatliquor effect.Secondly,the tall oil diethanol amide was obtained by using tall oil and diethanolamine,after being emulsified with hot water to obtain tall oil diethanolamide fatliquicide?N-TO?.The optimum reaction conditions were obtained by single-factor experiment which were the reaction time was 4 h,reaction temperature was 130?,molar ratio of tall oil to diethanolamine was 1: 1.Meanwhile,through the esterification and sulfitation of tall oil diethanol amide,diethanolamide succinic acid tall oil?SS-TO?was synthesized.The optimum reaction conditions of tall oil diethanol amide were that the reaction time was 5 h,reaction temperature was 150?,molar ratio of TO with diethanolamine was 1:1.The tall oil diethanol amide prepared under the optimum conditions was reacted with maleic anhydride and the optimum conditions were reaction time 2 h,reaction temperature 95?,n?OH?: n?maleic anhydride?was 1:1.Finally,Na2S2O5 was used to modify above-mentioned product,as a result,SS-TO was obtained.The exhaust of waste liquid waste and emulsification of product were as indexes,the best dosage of Na2S2O5 was 11.56%.The structure and properties of N-TO and SS-TO were characterized.The results showed that HLB values of N-TO and SS-TO were 11.2 and 12.0 respectively;the particle size of two fatliquors of wt 0.1% were 192.5 nm and 175.8 nm.N-TO emulsion had good resistance to chromium salt,tannin extract,alkali resistance,but poor acid resistance,while SS-TO emulsion took on good stability.The properties of leather before and after being fatliquered by N-TO,SS-TO and commercially available fatliquoring sulfonated oil SS were characterized.The results showed that the physical and mechanical properties were significantly increased.SEM results showed that the collagen fibers became looser.The comprehensive fatliquoring effect was excellent.Moreover,through the reaction of tall oil diethanolamide and phosphorus pentoxide,the phosphorylated tall oil?P-TO?was obtained after being neutralized.The structure and performance of the product was studied.The optimum reaction conditions were as follows: the reaction temperature was 80?,the reaction time was 3.5 h,the dosage of P₂O₅ was 10%,hydrolysis temperature was 70?,hydrolysis time was 2.5h,the dosage of water was 3%.The emulsification time of P-TO prepared under the optimum reaction conditions was the longest.The results showed that HLB value of P-TO emulsion was 13.0,the particle size of emulsion was 105.3nm,as well as the emulsion had good resistance to chromium salt,tannin,alkali,acid and centrifugal.The FTIR results indicated the formation of phosphate groups.The structure and properties of the leather before and after being fatliquored were characterized.The tensile strength and tear strength of fatliquored leather were significantly increased.SEM results showed that the collagen fibers become looser after fatliquoring.The comprehensive fatliquoring effect of P-TO was nearly same with NLM.Finally,a simple comparison had been made with four kinds of synthesized fatliquors.S-TO had the lowest cost,and its appearance of the market was more easily acceptable by factories.SS-TO and P-TO had the most wide application area;the combination force of P-TO with collagen fiber was the strongest,as well as it had the best biodegradability.