Synthesis of Trivinylisooctyl POSS and Its Application in UV-Curing of Polyurethane Acrylate Coatings
Rubén González-Núñez
Round 1
Reviewer 1 Report
Manuscript ID: coatings-1804690 entitled:
Synthesis of Trivinylisooctyl POSS and Its Application in UV-curing of Polyurethane Acrylate Coatings
Authors Yufeng Wang * , Zhenheng Cao , Ziheng Wang , Aijuan Ma
General comment
The paper presents a study regarding the synthesis of the modifier TVi7iso-POSS, used further with butyl methacrylate (BMA), dodecafluoroheptyl methacrylate (DFMA), difunctional PUAs (PUA-2), and photo-initiator 1173 to produce a novel polyurethane coating (PFMPUAs) via UV-curing. The performance of the obtained PFMPUA coating was analysed via X-ray photoelectron spectrometry, SEM, atomic force microscopy, TGA, and differential scanning calorimetry. Thermal stability, hardness, flexibility, impact resistance, and adhesion of the PUA coating were investigated.
Some recommendations and observation remain:
1. Specify the modality of deposition of film onto tin plate (doctor blade, spin coating, etc.)
2. In FT-IR spectra some peaks remain unattributed.
For example at around 1680 - 1620 (v) cm-1 and 917 cm-1 the alkenyl C=C stretch and respectively =C-H bend appear.
3. Compare the data obtained with some similar ones presented in the literature for other polyurethane coatings, in order to highlight the improvements made.
4. Check the references and choose a uniform style.
Author Response
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Author Response.pdf
Reviewer 2 Report
Title: Synthesis of Trivinylisooctyl POSS and Its Application in UV-curing of Polyurethane Acrylate Coatings
Dear Editor,
The manuscript by Wang et al reports the synthesis of Trivinylisooctyl POSS and its application in UV-curing of polyurethane acrylate coatings. I appreciate the opportunity to review this interesting manuscript. The authors should carefully revise and check the manuscript for any typos or mistakes. More specific comments are found below:
1- Please correct grammar mistakes and spelling errors.
For example: TVi7iso-POSS is a POSS derivative possessing three olefin and seven isooctyl bonds; its molecular structure was confirmed by FT-IR, 1H-NMR, and mass spectrometry.
Light transmittance characterisation of the PFMPUA coating
2- Please check all the usage of abbreviations in the text.
for example
First, the molecular structure of TVi7iso-POSS was characterised using FT-IR spectroscopy, 1H-NMR, and mass spectrometry (MS). The infrared spectrum was examined using a Fourier-transform infrared (FT-IR) spectrum analyser (SHIMADZU IRTracer-100 spectrometer, Japan).
3- In the introduction section, the novelty of the study and its superiority over other studies should be explained.
4-Information such as the purity and molecular weight of the materials should be included.
5-The materials and methods section should be clear with the amounts of materials.
6- The FTIR graph should be drawn in the frequency range of 400-4500 cm-1. And it should be explained in detail with references.
7- Please check Fig.8. There are meaningless shapes (line).
8- Experimental data have not been adequately discussed with previous studies. The authors should support the discussion with more references.
9- Conclusion re-written emphasizing on results and future directions
Author Response
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Reviewer 3 Report
This article is well established. Following corrections are needed for improvement.
11. Please rewrite the 1st sentence of abstract as it shows direct objective using ‘to’ andnd mentioned appropriate field of applications.
22. SEM images are required with these surface characterization and novelty of the method cannot be predicted good.
3. In TGA and DSC analysis line 228-232, authors stated “This is because the PFMPUA coating is a hot-curing coating, and its crosslinking degree increases as the TVi7iso-POSS content increases. However, because TVi7iso-POSS possesses seven isooctyl bonds, its introduction reduces the Tg of the PFMPUA coating. Use appropriate reference for justification. Similarly, for the sentence “This was because TVi7iso-POSS possesses only three olefin bonds” (line 259).
44. In method section, is there authors maintained any standard, if yes please mention the standard by
55. Rewrite the conclusion, such as authors mentioned in line 179 that the mechanism of the flu- 179 orine group shifting to the surface of the coating was not investigated further in this study; 180 however, it is necessary to investigate it in detail in future studies. This should be mentioned in conclusion very shortly.
Author Response
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Author Response File: Author Response.pdf
Reviewer 4 Report
The manuscript “ Synthesis of Trivinylisooctyl POSS and Its Application in UV-2 curing of Polyurethane Acrylate Coatings”, presents a series of experiments to determine an optimal method to modify the PUA coating–trifunctional group POSS. The performance of coating was analysed via XPS, SEM, TGA and DSC. The synthetic POSS improved the hardness, thermal stability and its flexibility of the PUA coating. The study is interesting and well conducted with sufficient experimental evidence. I suggest minor corrections:
1. Improve figure 7 C
2. Table 2 (check units of properties) sign of flexibility a 0
3. Impact resistance in cm?
Author Response
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Author Response File: Author Response.pdf
Round 2
Reviewer 2 Report
accept
This manuscript is a resubmission of an earlier submission. The following is a list of the peer review reports and author responses from that submission.
Round 1
Reviewer 1 Report
Comments to the Authors
This manuscript demonstrates the synthesis of trifunctional ethylene POSS followed by their coating and UV treatment. The obtained coated samples were characterized for their synthesis, morphology and thermal behaviors. The coating applications were also determined for mechanical and hydrophobicity.
The following important critical point I am going to arise
- The idea presented in the manuscript is in very poor language and contains a lot of typos and grammatical mistakes. These mistakes mislead the readers, for example, in line 79 the others said “. Its reaction equations are shown in Fig1”. I think this is just a single equation.
- The abstract of the paper is just describing the procedure of the experiments.
- Many chemical names or their abbreviations are very new to me and even not reported in the literature.
- The authors claimed sometimes their coatings with respect to TVPS% but sometimes with DFMA%, which creates a lot of confusion that one cannot follow the story of the manuscript.
- The authors also did not mention which specific coated samples they characterized for XPS, AFM etc analysis.
- The caption of figure 5 and figure 6 are wrong.
- Very limited previous literature data have been included.
- Many important properties of the coatings such as glass transition temperatures and melting point by DSC, mechanical properties, elongation properties, optical properties etc of the coated samples are missing.
Therefore, In the current form, I will not recommend this manuscript for publication in the journal of coatings.
Author Response
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Author Response File: Author Response.pdf
Reviewer 2 Report
Manuscript ID: coatings-1694087 entitled:
Synthesis of trivinyl POSS and its application in UV-curing coating.
Authors Yufeng Wang, Zhenheng Cao, Ziheng Wang and Aijuan Ma
General comment
The paper presents a study regarding the preparation and characterization of a fluoroacrylic resin (MPFPUAs). Hardness, flexibility, heat stability and adhesion of the MPFPUAs coatings were investigated.
Some recommendations and observation are listed below:
- Check the text, some words must be corrected, had to be written in capital letters (see authors), others in lower case (see triSilanolisooctyl, decdecfluoro heptan methacrylate, difffferential thermogram, etc ). Use the text the same notation (whole notation, not partial) for compounds. The abbreviation is a little difficult to follow.
Maybe a legend with all the abbreviations is welcome. Missing abbreviation for FPAPUAs.
In figure 1 put the abbreviation under reactants and product.
In figure 2 the notations are different from the text (BMA, FAPM?).
- In the Experimental section please mention the working wavelength, in the UV curing process.
The thermostability of the coating was measured in air or inert atmosphere?
- More details are request for adhesion tests of the UV-cured coatings and for tests of pencil hardness (were evaluated by an adhesion test machine according to the …… Standard ……. And a pencil hardness tester according to the…….Standard …….), detailed procedures for the tests were depicted in [publications]. Give also detailed aspects regarding mass spectrometry.
- Specify some characteristics for the polyurethane acrylate (PUA).
5.In the NMR spectrum, figure 4, extend the scale from 0-10 ppm. To demonstrate the disappearance of Si-OH signals, present the NMR spectra of triSilanolisooctyl POSS (ioc-T7(OH)3). Also, the referenced substance used in the NMR spectra, probably TMS, and the temperature of the recorded spectra, need to be written in the manuscript.
- The figure captions need to be interchanged, Figure 5 represents the mass spectra of ioc-TVPS, while Figure 6 reveals the actual apparent photograph of ioc-TVPS.
- It is the best to rewrite for clarity the entire experimental section taking in account the aforementioned aspects. Insert also a table with all investigated coating and their notation and formulations. At R151 the wide-scanning spectra and high-resolution spectra of the coating (MPFPUAs) are exhibited in Fig 7. But is not clear the composition of this coating. At R 185 FPAPUAs coating’s surface roughness was presented in figure 8, also the composition of this coating is not specified. The difference between these coatings is not specified in text.
In Figure 9 the TG and DTG curves of the coating with different TVPS contents are insert. All figures need a detailed coating description. Are the morphologies the same for all coatings?
- In figures 9 weight loss in % is represented on Y-scale. Use the same format axes in figures 9 (for X and Y scales).
- Mention in text the number of replicates for each determinations. Insert in Table 1 the incertitude parameter.
- In abstract at R15 “The results proved that the hardness, flexibility, heat stability and adhesion
of the MPFPUAs coating were improved distinguishably compared with previous coatings modified by single functional POSS or eight functional group POSS”, the flexibility is mentioned but further, in text no other results or comments regarding flexibility are presented.
Also, to sustain the affirmation, please insert the improvements brig by these MPFPUAs comparatively with previous one.
- Please check the figures 9 it seems that the E (15% TVPS) coating present the lowest residual mass loss at 800°C. Why? The residual mass should be higher or at least equal with coatings with TVPS lower than 15%. (If TG will be performed after 1000°C in air, the content of silica can be estimate and correlate with the theoretical one).
Author Response
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Author Response File: Author Response.pdf
Reviewer 3 Report
The article titled “Synthesis of trivinyl POSS and its application in UV-curing coating” by Wang et al. has been reviewed. This work presented the synthesis and characterization of trivinyl POSS and extended its application to UV -curing of coatings. The characterization processes used are detailed and systematic. The manuscript may warrant publication in Coatings however prior to that there are a few of the concerns to be addressed.
- The first point to note that the whole writes up needs brushing of English language.
- The title of the manuscript also needs to be revisited and it may be “Synthesis of trivinyl POSS and its application in UV-curing of coatings”.
- Using the full form of POSS in the title would make it more descriptive.
- Have the authors made any effort on determining the molecular weight of the synthesized product? There is no information on this and the molecular weight distribution.
- Also, there is information on the purity of the synthesized product.
- In Figure 3, assigning of the main peaks would be informative.
- In Figure 10, Weight contents vs contact angles are presented. Can the authors also present images of the drops on the coated surfaces that they have measured? For example, the Figure 9 of the article Applied Spectroscopy, 70(7), 2016, 1137-1149, DOI: 10.1177/0003702816652327 can be an example of how to do this. Another example can also be found at DOI: 10.7498/aps.65.134701
Author Response
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Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
After careful reading, I did not find any significance of the manuscript for publication in a reputed journal such as Coatings. The Idea presented is very poor. The results are not presented very systematically. The English language is so poor that anyone can find it from the title and abstract of the manuscript.
Although this is the 2nd time revision but the language presented is so poor. At least the authorts can do these corrections by some professionals or native speakers.
Author Response
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Author Response File: Author Response.pdf
Reviewer 2 Report
Manuscript ID: coatings-1694087 entitled:
Synthesis of trivinyl POSS and its application in UV-curing coating.
Authors Yufeng Wang, Zhenheng Cao, Ziheng Wang and Aijuan Ma
General comment
The paper presents a study regarding the preparation and characterization of a fluoroacrylic resin (MPFPUAs). Hardness, flexibility, heat stability and adhesion of the MPFPUAs coatings were investigated.
After revision, some recommendations and observation remain:
- Check the entire text, some words must be corrected, had to be written in capital letters, others in lower case, add spaces between words:
Some examples
- lower case in the middle of phrases:
- at R 140 “In FT-IR spectra of TSOHP, The peak at 2900 cm-1…”
- at R 143 “In FT-IR spectra of EMVS, The small peak at 3100 cm-1 is peak of (=C-H) of EMVS.
Capital letter at the beginning of phrase:
-R269 “ last but not least, the light transmittance of …”
-rewrite the sentences”
“In FT-IR spectra of TVSP, the stretching vibration peaks around 1650 cm-1 and 3100 cm-1 indicate presence of double-bond peaks, which due to the three olefin bonds on TVSP”
-space between word:
“The Figure 2A presents1H-NMR spectra of TSOHP”
- In the NMR spectrum, figure 2 at R 157 “The peaks at 6.5 are silicon hydroxyl peaks of TSOHP…”, and write the appropriate value and follow by unit (ppm).
- Specify some characteristics for the polyurethane acrylate (PUA) used.
- The entire paragraph 3.4 must be rewrite in a clearer manner.
In Figures 7 each figure must be notated (A, B and C) and give a detailed title.
For example Fig 7. A) TG thermograms, B) DSC curves and C) DTG curves of the coating with different TVSP contents.
Take in account that decomposition rate unit is %/min.
Authors write “ The weightlessness temperature is between 285℃ and 311℃…” what represent the weightlessness temperature and what mean that the weightlessness rate is 10% ?
The formulation of phrases is not good. In this case probable the author refers to the loss of mass (not speed!).
From the thermograms you can see the temperature at which the decomposition process of the compound takes place with a maximum rate.
For example from figure 7A, it can be seen that at ~ 400°C the decomposition process, take place with maxim rates (for all coatings).
TG analysis involves mentioning the temperature ranges where mass losses occur, what represent these mass losses, which is their cause (specify the nature of some bonds susceptible to broke in the mentioned temperature interval) and the residual mass value.
For example The compounds present a … % weight loss between … ..°C to …°C. In this temperature domain the weight loss is attributed to the loss of residual water or solvent (or some bond cleavage, or main polymer chain, etc)
- Remove so on from the phrases. In text, only concrete properties should be write, not in general.
R 279 “The synthesized TVSP can improve flexility properties, thermal stability, hardness and so on of ….”
R284 “The conclusion indications that trivinyl POSS has broad application prospects” needed to be reformulate. (The number of useful properties propertied found for trivinyl POSS point to a wide range of possible application in industries.)
- Check the references and correct mistakes:
For example
[3] abbreviation ACS Appl. Mater. & Interfaces 2021, 13, 58193–58200, https://doi.org/10.1021/acsami.1c18226
Author Response
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Author Response File: Author Response.pdf
