Progress 09/01/08 to 08/31/13
Outputs
Target Audience: U.S. corn growers will be the immediate beneficiaries of the investigation by finding new value-added uses of cornstarch derivatives in adhesive market which is dominated by petroleum-based products. The intended starch-based curing agents and crosslinkers are water soluble, non-toxic and cost effective. They could become valuable environmentally benign alternatives to urea-formaldehyde resins or even phenol-formaldehyde resins. The general public will benefit from the results, because starch-based curing agents and crosslinkers are environmentally friendly and energy efficient, and provide solutions for formaldehyde-free and and low VOC emission wood products. In addition, the findings from this project will advance the bioplastics knowledge base and stimulate future developments within the biobased plastic materials industry. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? The postdoc (Pei Zhang) and the graduate student (Jia Cheng) attended the 2013 Spring ACS meeting in Indianapolis and presented their research. How have the results been disseminated to communities of interest? Oral presentations were given to dissemenate the information as follows: 1. Starch-based curing agents for waterborne epoxies, 2010 International Wood Composite Symposium, Seattle, March 29 – 31, 2010. 2. Use of lignin as feedstock for epoxy application, 2013 International Wood Composite Symposium, Seattle, WA, April 3-4, 2013 3. Diversifying renewable feedstocks for new biobased polymers and applications, 2012 BioEnvironmental Polymer Society Meeting in Denton, Texas, Sept. 18-21, 2012. 4. The First International Symposium on Polymer Ecomaterials, Changchun, Jilin, China, Aug. 19 - 23, 2012. 5. Development of a novel processing method for high performance residual biomass-based polymer blends, 2012 Corn Utilization and Technology Conference, June 4 -6, 2012, Indianapolis, IN. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Following our plan, we have made significant achievements on the synthesis of starch-derived curing agents and assessment of their applications for wood composite adhesives. We investigated the preparation of starch-derived epoxy curing agents and crosslinkers for wood composites. Starch and hydrolyzed starch (i.e., dextrin) were used as the feedstock, and the preparations of derivatives containing carboxylic acid groups and amino groups were studied in several preparation methods. Such derivatives were then used to cure waterborne epoxies and the adhesion properties of the resulting resins were evaluated. Specifically, the major activities include the following: I. Investigated various syntheses for starch/dextrin-derived polycarboxylic acids a. Polycarboxylic acids based on esters of trimellitic anhydride and dicarboxylic acid from the conversion of vic-diols; b. Effects of reaction conditions on degree of substitution (catalyst, temperature, concentration, etc); II. Investigated the syntheses of starch/dextrin-derived polyamines a. Polyamines based on reductive amination of dialdehyde starch/dextrin; b. Effects of reaction conditions including temperature, concentration, reductant, etc); III. Studied the curing of waterborne epoxies using the starch/dextrin-derived polyacids and polyamines IV. Assessed the adhesive applications of the obtained polyacids and polyamines in waterborne epoxy resins for wood bonding V. Developed a novel starch derivative that exhibited great adhesion properties when cured with plant proteins or polyamine compounds. We identified that the starch-derived polycarboxylic acid based on esters of the trimellitic anhydride presented to be effective waterborne curing agents and the resulting resins demonstrated excellent adhesion properties under both dry and water soak-and-dry environments. The starch-derived polyamine curing agents also presentedas good waterborne curing agents and the resulting resins exhibited decent adhesion properties under dry condition but poor adhesion under water soak-and-dry tests. Furthermore, a novel starch-derivative which can be cured with amino-containing materiasl such as protein and polyimine was synthesized and the cured resins exhibited excellent adhesion properties under both dry and water soak-and-dry conditions. Historically, starch-based glue or binder has been used for textiles and carton boards. Nonetheless, they usually present insufficient adhesion and poor water resistance and are not suitable for engineering applications. In this project, the means to turn starch into advanced adhesive systems was novel and creative. By using starch hydrolysate as feedstock, polycarboxylic acids, polyamines and polyphenol were prepared. While the first two can be used as curing agents to cure waterborne epoxies, the latter can be used for novel adhesives in combination with polyimines or plant proteins.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
Xiaoqing Liu; Yi Wang; Yang Cao; Vikram Yadama; Ming Xian; Jinwen Zhang. Study of dextrin-derived curing agent for waterborne epoxy adhesives, Carbohydrate Polymers 2011, 83, 1180 1184.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2014
Citation:
Pei Zhang; Jinwen Zhang. Synthesis of starch-based high performance adhesive systems
- Type:
Other
Status:
Under Review
Year Published:
2014
Citation:
Jinwen Zhang; Pei Zhang. Novel starch derivatives for high performance adhesives (disclosure of intellectual property)
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Progress 09/01/11 to 08/31/12
Outputs
OUTPUTS: For the past year, the research was focused on methods for improving the degree of carboxylation of the starch-based polyacrylic acid (SPAA) type curing agent and introducing amino groups into starch for starch-based polyamine or polyacylamide (SPA or SPAM) type curing agent. Curing reactions and adhesion properties of the waterborne epoxies cured using the obtained curing agents were also evaluated. Specifically, analysis was conducted as follows: 1. Investigation of novel carboxylation methods of starch/dextrin. a. Methods of introducing polyacrylic acid into starch and dextrin by polymerization reaction. b. Effects of reaction conditions on degree of substitution (procedure, temperature, concentration, etc.) 2. Investigation of novel amination methods of starch/dextrin. a. Methods of introducing amino groups into starch and dextrin by Michael reaction or esterification. b. Effects of reaction conditions on reaction effectivity (aminating agent, amination reaction type, etc.) 3. Adhesive application for waterborne epoxies for wood bonding. a. Investigation of dextrin-derived SPCA for waterborne epoxy curing. b. Study the formulation of SPCA curing agent used for waterborne epoxy curing. We have disseminated the outputs by publishing one paper and are preparing two other manuscripts. One invited presentation was given to a workshop hosted by the University of Minnesota in June 2011; one invited presentation was given at the 2012 BioEnvironmental Polymer Society Meeting in Denton, Texas, September. PARTICIPANTS: Dr. Jinwen Zhang (PI), provides project management and oversight while participating in the investigation of all three specific aims defined in the proposal. Dr. Zhang directly advises his PhD student and postdoc working in this project, and sometimes was physically involved in the experiments. Dr. Ming Xian (co-PI), participated in the investigation of Specific Aim #1 (Synthesis). Dr. Vikram Yadama (co-PI), participated in the investigation of Specific Aim #3 (Adhesive Application). Dr. Pei Zhang, postdoctoral research associate, worked on synthesis of the curing agents and the structure-curing-property relationship of the cured epoxy using the synthesized curing agent (Specific Aims #1 & 2: Synthesis and Characterization). Mr. Yi Wang, PhD student (graduated in 2012), participated in the study of Specific Aim #3. Miss Jia Cheng, PhD student, participated in the study of Specific Aim #1. TARGET AUDIENCES: U.S. corn growers will be the immediate beneficiaries of the investigation by finding new value-added uses of cornstarch derivatives in adhesive market which is dominated by petroleum-based products. The intended starch-based curing agents and crosslinkers are water soluble, non-toxic and cost effective. They could become valuable environmentally benign alternatives to urea-formaldehyde resins or even phenol-formaldehyde resins. The general public will benefit from the results, because starch-based curing agents and crosslinkers are environmentally friendly and energy efficient, and provide solutions for formaldehyde-free and and low VOC emission wood products. In addition, the findings from this project will advance the bioplastics knowledge base and stimulate future developments within the biobased plastic materials industry. PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
The studies proposed under all three specific aims (synthesis, evaluation of structure-property relationship and adhesive application) in the proposal were performed. As mentioned last year, some obstacles were met. The degree of carboxylation of dextrin was limited and the blocking of some of the hydroxyl groups via acetylation led to the reduction of the solubility of the resulting curing agents. To overcome these problems, a new approach of introducing carboxylic acid groups into starch/dextrin was designed. In this effort, the hydroxyl groups in dextrin were all blocked by acrylation, followed by free radical graft polymerization with acrylic acid. The water soluble carboxylic acid groups in SPAA are expected to be converted into water insoluble ester groups after the curing reactions. The acrylation of dextrin has been realized successfully. The polymerization conditions between dextrin acrylate and acrylic acid are still in exploration. In addition to the carboxylation of dextrin, introducing amino or acylamide groups into dextrin were also attempted. Glycine was employed in an attempt to acylate the hydroxyl groups in dextrin. Several catalysts and solvents were tested in this reaction. The insolubility of glycine and dextrin in non-aqueous solvents was the major problem in this approach. Based on the Michael Addition of hydroxyl groups by acrylonitrile, nitrile groups were introduced into dextrin. Nitrile groups could be converted to acylamide by basic hydrolysis, or amino groups by hydrogenation. The reaction conditions of obtaining acylamide or amino groups are under investigation.
Publications
- Diversifying renewable feedstocks for new biobased polymers and applications, Abstract, in 2012 BioEnvironmental Polymer Society Meeting in Denton, Texas, Sept.18-21, 2012.
- Xiaoqing Liu, Yi Wang, Yang Cao, Vikram Yadama, Ming Xian, Jinwen Zhang. Study of dextrin-derived curing agent for waterborne epoxy adhesives, Carbohydrate Polymers 2011, 83, 1180-1184.
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Progress 09/01/10 to 08/31/11
Outputs
OUTPUTS: For the past year, the research was focused on methods improving degree of carboxylation for the starch-based polycarboxylic acid (SPCA) type curing agent and improving the water resistance by blocking some of the unreacted hydroxyl groups. Curing reactions and adhesion properties of the waterborne epoxies cured using the obtained curing agents were also evaluated. 1. Investigation of carboxylation and acetylation methods of starch/dextrin a. Effects of catalyst type on carboxylation and etherification of starch and dextrin b. Effects of reaction conditions on degree of substitution (temperature, concentration, etc.) 2. Adhesive application for waterborne epoxies for wood bonding a. Investigation of dextrin-derived SPA for waterborne epoxy curing. b. Study of adhesion properties. PARTICIPANTS: Dr. Jinwen Zhang (PI), oversees the whole project and participate in the investigation of all three specific aims defined in the proposal. Dr. Zhang directly advises his PhD student and the postdoc working on this project, and sometimes is physically involved in the experiments. Dr. Ming Xian (co-PI), participated in the investigation of specific aim #1 (synthesis). Dr. Vikram Yadama (co-PI), participated in the investigation of specific #3 (adhesive application). Dr. Pei Zhang, postdoctoral research associate, worked on synthesis of the curing agents and structure-curing-property relationship of the cured epoxy using the synthesized curing agent (Specific Aims #1 &2: Synthesis and Characterization). Mr. Yi Wang, PhD student, participate in the study of specific aim #3. Miss Jia Cheng, PhD student, participated in the study of specific aim #1. TARGET AUDIENCES: U.S. corn growers will be the immediate beneficiaries of the investigation by finding new value-added uses of cornstarch derivatives in the adhesive market which is dominated by petroleum-based products. The intended starch-based curing agents and crosslinkers are water soluble, non-toxic and cost effective. They could become valuable environmentally benign alternatives to urea-formaldehyde resins or even phenol-formaldehyde resins. The general public will benefit from the results, because starch-based curing agents and crosslinkers are environmentally friendly and energy efficient, and provide solutions for formaldehyde-free and and low VOC emission wood products. In addition, the findings from this project will advance the bioplastics knowledge base and stimulate future developments within the biobased plastic materials industry. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The studies proposed under all three specific aims (synthesis, evaluation of structure-property relationship and adhesive application) in the proposal were performed. Particularly, SPCA was prepared using dextrin (hydrolyzed starch) as feedstock, and carboxylation of dextrin was carried out by reacting with maleic anhydride and trimellitic anhydride. Blocking part of the hydroxyl groups of dextrin was studied in an attempt to increase the water resistance of the cured resins. Waterborne epoxy cured by the carboxylated dextrin with trimellitic anhydride demonstrated almost an identical adhesion strength as phenol formaldehyde (PF). However, after water-soaking-and-drying test, the former displayed inferior strength than the latter. We considered the poor water resistance was mainly attributed to the higher hydrophilic of the cured waterborne epoxy with respect to that of cured PF resins, because there were still a significant amount of unreacted hydroxyl groups in dextrin. Besides making effort to increase the degree of carboxylation, blocking some of the residual hydroxyl groups in dextrin was also studied. Nevertheless, some obstacles were met. Degree of carobxylation was limited and blocking some of hydroxyl groups via acetylation led to the reduction of the solubility of the resulting curing agents. We are still trying to solve these problems and dilemmas. We have published one paper this year and are preparing another one. One presentation was giving to a workshop hosted by University of Minnesota in June 2011. We will also present our results in the coming 2012 ACS spring meeting.
Publications
- Xiaoqing Liu, Yi Wang, Yang Cao, Vikram Yadama, Ming Xian, Jinwen Zhang. Study of dextrin-derived curing agent for waterborne epoxy adhesives, Carbohydrate Polymers 2011, 83, 1180 - 1184.
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Progress 09/01/09 to 08/31/10
Outputs
OUTPUTS: In the past year, we have focused our study on synthesis of starch-based polycarboxylic acid (SPCA) type curing agent for waterborne epoxies, and subsequently investigated the curing behavior and adhesion application of the prepared waterborne epoxy curing agent. 1. Investigation of carboxylation methods of starch/dextrin: a. Effects of catalyst type on degree of substitution, b. Effects of reaction conditions on degree of substitution (temperature, concentration, etc.); 2. Adhesive application for waterborne epoxies for wood bonding: a. Investigation of dextrin-derived SPA for waterborne epoxy curing, b. Study of adhesion properties - comparison with phenol formaldehyde. PARTICIPANTS: Dr. Jinwen Zhang (PI), supervised the whole project and participated in the investigation of all three specific aims defined in the proposal. Dr. Zhang directly advised his PhD student and postdoc working on this project, and sometimes was directly involved in the experiments. Dr. Ming Xian (co-PI), participated in the investigation of specific aim #1 (synthesis). Dr. Vikram Yadama (co-PI), participated in the investigation of specific aim #3 (adhesive application). Dr. Xiaoqing Liu, postdoctoral research associate, worked on synthesis of the curing agents and structure-curing-property relationship of the cured epoxy using the synthesized curing agent (Specific Aims #1 &2: Synthesis and Characterization). Mr. Yi Wang, PhD student, participated in the study of specific aim #3. TARGET AUDIENCES: U.S. corn growers will be the immediate beneficiaries of the investigation by finding new value-added uses of cornstarch derivatives in the adhesive market, which is dominated by petroleum-based products. The intended starch-based curing agents and crosslinkers are water soluble, non-toxic and cost effective. They could become valuable environmentally benign alternatives to urea-formaldehyde resins or even phenol-formaldehyde resins. The general public will benefit from the results, because starch-based curing agents and crosslinkers are environmentally friendly and energy efficient, and provide solutions for formaldehyde-free and low VOC emission wood products. In addition, the findings from this project will advance the bioplastics knowledge base and stimulate future developments within the biobased plastic materials industry. PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
The studies proposed under all three specific aims (synthesis, evaluation of structure-property relationship and adhesive application) in the proposal were performed. Particularly, SPCA was prepared using dextrin (hydrolyzed starch) as feedstock, and carboxylation of dextrin was carried out by reacting with maleic anhydride and trimellitic anhydride. Some very encouraging progress has been made. Waterborne epoxy cured by the carboxylated dextrin with trimellitic anhydride demonstrated almost identical adhesion strength as phenol formaldehyde (PF) which is one of the most used adhesives in forest products. On the other hand, after the water-soaking-and-drying test, the former displayed inferior strength than the latter. The reason was mainly attributed to the higher hydrophilicity of the cured waterborne epoxy with respect to that of cured PF resins. We will continue to look for solutions to overcome this problem by increasing the degree of substitution or blocking some of the residual hydroxyl groups in dextrin.
Publications
- Xiaoqing Liu, Yi Wang, Yang Cao, Vikram Yadama, Ming Xian, Jinwen Zhang. Study of dextrin-derived curing agent for waterborne epoxy adhesives, Carbohydrate Polymers 2010, Doi: 10.1016/j.carbopol.2010.09.019
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Progress 09/01/08 to 08/31/09
Outputs
OUTPUTS: This project was planned to start in September 2008. In fact, we just started it from the beginning of this year. We have recruited a postdoctoral research associate working on it, and we will put another PhD graduate student in fall 2009 working on it. At this point, we do not have substantial amount of data to report. PARTICIPANTS: Dr. Jinwen Zhang (PI), oversees the whole project, directly advises his PhD student and postodc working in this project, and sometimes physically involves in the experiments. Dr. Ming Xian (Co-PI), participate in the investigation of specific aim #1. Dr. Xiaoqing Liu, postdoctoral research associate, working on synthesis of the curing agents and structure-curing-property relationship of the cured epoxy using the synthesized curing agent (Specific Aims #1 &2). TARGET AUDIENCES: U.S. corn growers will be the immediate beneficiaries of the investigation by finding new value-added uses of cornstarch derivatives in adhesive market which is dominated by petroleum-based products. The intended starch-based curing agents and crosslinkers are water soluble, non-toxic and cost effective. They could become valuable environmentally benign alternatives to urea-formaldehyde resins or even phenol-formaldehyde resins. The general public will benefit from the results, because starch-based curing agents and crosslinkers are environmentally friendly and energy efficient, and provide solutions for formaldehyde-free and and low VOC emission wood products. In addition, the findings from this project will advance the bioplastics knowledge base and stimulate future developments within the biobased plastic materials industry. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
N/A
Publications
- No publications reported this period
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