東京理科大学「火災安全科学研究拠点」
Tokyo University of Science “Research Center for Fire Safety Science”■研究成果概要報告書/ Report for Outline of Research Results

研

究 課 題

Research Topic所属
研究代表者

Affiliation

Research

氏名LeaderNameDevelopment of new flame retardant andthermal stabilizers for polymers
Especially used in buildings and construction
applications

実施年度

2016

Department of Chemistry, Chuadhary Charan Singj
University, Meerut, India
Rakesh Kumar Soni

e-mailRksoni_rks@yahoo.com

受入担当責任者

氏名

Takashiro Akitsu

Organizatio

Namen
１．研究の背景および目的/ Background and Aim of Research

The objective of this ongoing research project was to prepare new thermal stabilizers for PVC(polyvinyl chloride) which shall be heavy metal free and shall be fire resistant and generates low
smoke. PVC is commodity plastic which is used in the building as cables/ doors/windows etc. The
PVC compounding force us to add heavy metal compounds such as Lead or cadmium compounds
which generates heavy metal dangerous compounds on heating or burning. It is necessary to findalternative thermal stabilizers which should be free from heavy metals or does not produce toxic
compounds during burning or heating. The principal investigator was interested to prepare newthermal stabilizers which should be heavy metal free and generates less toxic gases on heating orcombustion. The research project was adopted for the financial year 2016-17.

２．利用施設及び利用日/ Facility and Schedule
・ ●●装置 （2016 年--月--日～ --月--日）1.4.2016
・ ●●装置 （2016 年--月--日～ --月--日）31.3.2017
The following facilities of Department of Chemistry, Chaudhary Charan SinghUniversity, Meerut were utilized:1. Two roll mill
2. Compression Molding press
3. Tensile Strength Testing Machine
4. Differential Scanning Calorimeter
5. FTIR
6. HPLC
7. Reaction assemblyThe following facilities of Tokyo University of Science were used:1. TGA
2. Cone Calorimeter
3. Reaction facility
In addition the samples were sent for testing to M/S Hitachi High techLaboratory situated in Tokyo, Japan. Prof Akitsu and Prof. Soni visited twice
their laboratory but due to breakdown of the instrument the required testingof evolved gas analysis could not be made. On receipt of these results,
another research paper will be completed.

３．実験方法・研究成果、および考察（申請時の計画に対する達成度合いも含む）※継続課題の場合は，前年度との関係性，進展度合いについても記載すること。
/ Method, results, and conclusions (degree of achievement compare to application)
In the first year of the project Prof. R. K. Soni visited Tokyo University of Science to conduct
research work in collaboration of Prof T. Akitsu twice. Prof. Soni prepared several aromatic amides
in his laboratory in Charan Singh University, Meerut, UP India by the reaction of ammonia andamines with PET waste. Different aromatic amides prepared by Prof Soni and his team are as
follows:-Synthesis and Characterization of NN’ substituted terephthalamides
N,N’ bis-methyl terephthalamide, N,N’ bisaminoethyl terephthalamide, N, N’
bis-hydroxoethyl terephthalamide, N, N’-bis-n-butyl terephthalamide and terephthalicdihydrazide have been synthesized through aminolysis of PET waste with methylamine, ethylenediamine, ethanolamine, butyl amine and hydrazine hydrate at ambientconditions of temperature and pressure. The aminolysates have been characterizedthrough different spectroscopic and other analytical techniques.
Determination of Calorific Value of Terephthlamides
Calorific values of terephthalamides have been evaluated to suggest another applicationof these aminolysed end products by complete burning of a unit mass of the amide withoxygen at constant volume process. The heat of combustion of terephthalamides havebeen determined using Scientech digital Bomb calorimeter (an adiabatic system)
calibrated with benzoic acid. Standard calorific values of benzoic acid, ignition thread
and wire were used to calculate the water equivalent, whose value was used todetermine the calorific values of different terephthalamides by measuring thetemperature rise on combustion.

Calculation of Calorific values
Bomb calorimeter was standardize with benzoic acid and water equivalent (W) was
determined using standard calorific values of the nichrome wire and cotton thread; 350
cal/gm and 4200 cal/gm respectively. Calorific values of different aminolysates werecalculated by using the recorded ∆t values using the following expressions:𝑊𝑊 =6319𝑋𝑋𝑋𝑋𝑋𝑋𝑋𝑋𝑋𝑋ℎ𝑡𝑡 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎+(𝐸𝐸1 +𝐸𝐸2 )𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝑟𝑟𝑖𝑖𝑖𝑖𝑖𝑖………………………….Eqn 1

𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 =𝑊𝑊𝑊𝑊∆t−(𝐸𝐸1 +𝐸𝐸2 )𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡……………………………..Eqn2Where 6319 cal/gm is the calorific value of benzoic acid, E1 (Standard CV of wire X
weight of wire consumed) and E2 (Standard CV of thread X weight of cotton threadconsumed) are the calorific values of wire and cotton thread. W was calculated (2538.78cal/0C) and used to calculate the calorific values of terephthalamides through equation
2.
3 MS and TGA Characterization
Simultaneous TGA/DTA thermograms were recorded on Perkin Elmer, Diamond
TG/DTA at 20.00 0C/min in nitrogen atmosphere from 40 to 7000C. MS spectra wererecorded on Waters, Q-TOF Microma SS (LCMS) mass spectrometer.
These prepared aromatic amides were used in the preparation of PVC sheets. All aromatic amides
were successfully used as thermal stabilizers and smooth PVC sheets filled with different aromatic
amides were casted with the help of two roll mill and Compression Moulding press.

Casting of PVC sheet
PVC compounding was prepared in an internal batch mixer by taking plasticizer, filler,stabilizer, processing aids etc. with PVC resin. All the ingredients except plasticizer
were mixed thoroughly at 60-70 0C. The required amount of plasticizer was then added
to the mixture and mixed again thoroughly. During mixing, temperature was raised up
to 110 0C. Formulation comprises PVC resin 100 phr, DOP 50 phr, CaCO3 15 phr,stearic acid 1 phr and terephthalamide 10 phr. PVC formulation was processed by tworoll mill at the temperature of 144 0C for roll 1 and 146 0C for roll 2. Finally the PVC
sheet was prepared by using compression moulding machine by keeping temperature ofcompression plates at 142 0C (lower) and 145 0C (upper) with holding time of 1.5
minutes and cooling time of 1 minute.

Prof Soni brought all the PVC sheets to Tokyo University of Science during his first visit and it wasplanned to test these PVC sheets for TGA and burning experiments. During this visit, Prof. Akitsu
and his team prepared few complexes designated as Br0, Br1 and Br2 and given to Prof Soni for thepreparation of PVC sheets. These complexes were also used successfully and PVC sheets filled withthese complexes were prepared by Prof. Soni in this laboratory. The PVC sheets were also tested fortheir mechanical properties at CCSU Meerut, India.

TGA/DTA and Cone calorimetric analysis of PVC sheet
Simultaneous thermo gravimetric analysis (TGA) and differential thermal analysis(DTA)
thermogramsofPVC
sheet
wererecordedon
BrukerAXS.MS9610/DSC3200A/TG-DTA 2010SA under nitrogen atmosphere in thetemperature range of 25-450 0C at heating rate of 20 0C/ min. Flammability test wasperformed using the Cone Calorimeter III C3 ISO5660-1. Flat sample with size 10×10cm and thickness 2.5 mm was tested with radiation amount of 50.00 kW/m2 and heatertemperature of 761.2 0C. Sample was kept at a distance of 25 mm from cone and tested
for 753 seconds (12.54 min).
Cone calorimeter data and thermogravimetric analysis has been used to investigate thethermal behaviour of terephthalamide stabilized PVC sheet under irradiation heat fluxof 50 kW/m2. PVC sample undergoes single step thermal degradation with peakmaxima at 285.56 0C. The sample shows high value for flashover propensity whichindicates high level of risk however the total heat released suggests intermediate levelof risk. The PVC sheet was well stabilized thermally and hence efforts should be madeto overcome the problem of heat release to convert PVC sheet to be safe forconstruction applications.

Prof. Soni and Prof Akitsu also visited Hitachi Laboratory in Tokyo for conducting experiment forevolved gas analysis. The PVC samples were handed over to Mr. Obuko for testing. Unfortunately
the testing could not be completed for break -down of the instrument.
During second visit of Prof Soni to TUS Tokyo, Japan, the PVC sheets(Br0, Br1 and Br2) preparedin his laboratory were handed over to Prof. Akitsu for testing by TGA and for burning experiment.
Prof Soni and Prof akitsu visited Hitachi laboratory and Research Center for Fire Safety Science for
conduct of experiment. The TGA and burning experiment were conducted on PVC sheet filled with
TP10. A research paper was also written which has been accepted for publication in Journal of
Scientific and Industrial Research.
During first year of project, all the objectives were achieved however all the PVC sheets could
not be tested due to shortage of time and non-availability of the instruments.

４．今後の展望（今後の発展性，見込み等についても記述）/ Future Perspectives
In the next year 2017-18, more PVC sheets will be prepared by adding different aromatic amides
and Br complexes. Such PVC sheets will be tested for burning experiments and evolved gas
analysis. The mechanical properties of these sheets will also be determined. Such PVC sheets will betested for flame resistance and smoke generated during burning of the samples. It will also beevaluated for toxic gases.
５．成果の公表状況（学会への発表，学術誌への投稿等を記述。予定も含む）/ Publishing (presentation, paper, etc. incl. plans in the future)
In 2016, we have carried out some preliminary experiments and will publish one book chapter(whole research concept) and at least two original research papers.
[Book chapter] T. Akitsu, R. K Soni et al., “Dual Purpose Bromine-containing Schiff base Cu(II)Complexes for DSSC Dyes and Polymer Flame Retardants” in Hybrid Systems: Performance,Applications and Technology, Nova Science Publishers, Inc (NY, USA), in press.

Research Papers:- The following two research papers are prepared out of the research work
conducted in the last year. One research paper has been communicated to the journal for publicationand the other research paper is under preparation.

1. T. Akitsu, R. K Soni et al “TGA decomposition and Flame profile measurement ofTerephthalamide stabilized PVC by Cone calorimeter” Accepted for publication in
Journal of Scientific and Industrial Research.
2. T. Akitsu, R. K Soni et al “Studies of aromatic amide stabilized PVC sheet” underpreparation.
６．経費の使用状況/ Usage of Budget

expendables・Meeting・Travel expense

Personnel expenses

Printing
Contents

Cost

Contents

Cost
286,080

Chemicals

15,752

Airfare,

Book

2,160

Accommodati

Experimental
material
SubtotalContents

Cost
0on,
196,008
213,920

Road Travel
Subtotal

286,080Subtotal

Burden of Tokyo University of Science / Total Yen500,000 yen
Burden of _______ / Total Yen0