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CSS NITROPOLYMER RESEARCH Contract Nonr-l205(00)

V" w& January 1, 195U to March 31, 1?5U

Sag ga^il

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(OMMEWCIAI, SOLVENTS (UKPORATION

: t-< tr- iirtu i c . • J

Tr.LE"HONI CRAWPQ0O V C) 7 T IN P^Fiv orr*» TO

April 5, 195U Copy No. 25

Report No. Q-y (Quarterly Summary)

SUBJECTS ONR Nitropolyaer Research

CONTRACT: Nonr-I205(00)

PXRIOD COVERED

January 1, 195U to March 31> 19?U

WRITTEN BY s

APPROVED BY:

J^R•. / JlldaaadL "7* John 7. lttnor

A Chief Investigator

JTMM/^ s~t Jerome Martin

(^/Director of Research

Shis document contains infoTSfitioa affecting the national defence of the United States within the meaning of the Espionage LawSj Title 18. U.S.C-., Sections 793 and 79ii. The transmission or the revelation of its contents in any manner to an unauthorized person is prohibited by law.

CONFTDENfXAM A A "^WWwaaswiBgijaww' **»<**

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COMMERCIAL SOLVENTS CORP.

CONFIDENTIAL

Report No. Q-9

TABLE OF CONTENTS

Page

Contract Fulfillment iii

I. SUMMARY ................ 1

II. TECHNICAL PROGRESS .................... 1

A- Introduction . . . ...........* 1

B. Acrylyl Chloride ................... 2

C. 2,2-Dinitropropyl Acrylate .............. 2

D. 2,2-Dinttropropanol 2

'•

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COMMERCIAL SOLVENTS CORP.

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CONTRACT FJLFILLMEN?

Report No. Q-9

This quarterly report is submitted, in partial fulfillment of

Contract Nonr-l2o5fOO).

CONFLDENTIAL iii

.

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COMMERCIAL SOLVENTS CORP. Report No» Q~9

I. SUVl'ARY

A. This quarterly report is the third under Contract Nonr-l205(00) and covers the period from January i^ 19$h to March 31i 195h° The object of the contract is: Conduct research is the synthesis of polynitro com- pounds to include, but not necessarily be limited to, a review of the ch.errd.stry and the processes of preparation of the m^re usefu«. products of research from the nitropclymer program and investigate tivr applications of processes not now employed in the preparations.

B. The more important results and conclusions of the work of the quarter are presented be]ow,

1. Of the methods for preparing acrylyl chloride, that using acrylic acia and benzoyi chloride appears to be the most feasible.

2. The dinitropropyl acrylate process might be improved slightly by adding the aluminum chloride to the mixture of dinitropropanol and acrylyl chloride.

3. Silver nitrate recovery in the Shechter-Kaplan reaction will be good if all mechanical loss is avoided. This is true only if the un- reacted silver ions are recovered from the reaction solution, preferably by strong base.

h~ In the preparation of dinitropropanol by the Shechter-Kaplan reaction, there is little effect on yield from wide ranges of reaction tempera- ture or time.

f |

tl. TECHNICAL PROGRESS

A. INTRODUCTION

The principal effort during the quarter has been to review the processes leading to poly dinitropropyl acrylate. This effort led to a re- examination of the processes available for the preparation of acrylyl chloride, dinitropropanol, and dinitropropyl acrylate.

D. ACRYLYL CHLORIDE (AC)

As reducing the cost of AC appears to be the most promising point to start for reducing the cost of DNPA, the processes by which AC can be made were reviewed briefly, A co parison of several procedures was made by C. H. Stempel et al (1) and the r«action of benzoyi chloride with acrylic acid was favored over that of acrylic acid with thionyl chloride„ phosphorus oxychloride, phosphorus trichloride, or phosphorus pentachloridc- Attempts to repeat their work fell short of obtaining the reported yield of 68-72/6 by about l5%„

Two other procedures which can be handled In the laboratory, namely from ^-propiolactone through ^-chloropropionyl chloride (2), and from sodium acrylate wL'h phosphorus oxychloride (3), present handling and hazard diffi- culties wha ?h decrease their ease of scale-up

A British patent, (U) presents * process of passing chlorine and acrolein through a hot quarts tube and reports giving a "good yield", It is an interesting potential process but no laboratory work is contemplated at this time-

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COKMEP.CIAL 3QLTBKT3 CORF, Report No. Q-9 Page 2

Due to the percentage of chlorine present in benzotrichloride, it appears to be an economical chlorinating agent- When it. was used; a 37? yield of redistilled acrylyl chloride was obtained, The reaction was run in 100 gramd of Dowtherm U3ing 1.0 nole of acrylic acid and 0.$0 mole of benzotrichloride, Two 3imilar runs were made without a solvent and as soon as the reaction mixture reached 60-70°C:. polymerization set in.

As oenzoyl chloride and acrylic acid are both commercially avail- able and the process utilizing these starting materials presents fewer pro- duction problems, it would be favored at this tiiae for the preparation of AC<-

C. DDNITROfROPYL ACRYLATE (DNPA)

Since the preparation of DNPA in several run3 in cur pilot plant study was erratic in respect tc yield (5) we have reviewed the process is an attempt to eliminate some loss* In the process as used, the aluminum chlor- ie was added to the dinitropropanol (DPL) solution and the temperature raised to l45°C, followed by the addition of the acrylyl chloride (AC) solu- tion o It was suggested (6) that since the complex formed between aluminum chloride and DPL promotes decomposition on prolonged neating it might be better to add the aluminum chloride to the AC solution. Attempts to do this resulted in lower yields and a darker colored product. As the aluminum chlor- ide is detrimental to both reactants it was concluded that this ahould be the last material to be added to the reaction. Runs have been made in which the aluminum chloride was added to the solution of AC and DPL in ethylan's di- chloride, initially at room temperature. Some rate data were obtained with various ratios of catalyst as shown in Figures 1 and 2. These figures plot the hydrogen chloride liberated aiid swept from the reaction flask into stand- ard base against time. Ressults indicate that a 0.20 mole quantity of aluminum per mole of reactants ir> .'sufficient to give a complete reaction in 1-3A hours at 50°C. This prccedtuf** improves the color of the final product slightly and yields compare favorably to those for the original process.

In an attanrpc to find a purification procedure that eliminated the many washings .vhere our loss of product was high, steam distillation TTSS again tried. The reaction mixture can be steam distilled directly to remove the solvent and the DNPA. However the amount of steam required is high, at least 30 lbs. per lb. of product, and recoveries are not complete. Steam

, distillation at reduced prsssurs ~ss not appreciably different from that at normal pressure. It would be very desirable to isolate the product in this manner as loss and labor could be reduced; however, it is nut recommended as a process at this time.-.

D. DINITROPROPAN'OL (DPL)

If the cost of ac;ylyl chlovide can be reduced considerably, cl- an esteri/'i cation process developed in which acrylic acid is used, the majoi cost item in DNPA production would then be DPL. We have reexamineu the process used in its preparation to see if it is possible to lower the sliver nitrate loss, increase yield, and to determine the limits of the process conditions. Table I summarizes this work using DPL and S^-dinitropropanedio1

as reaction products. These eU\t& show that the major quantity of the silver not reduced "In the reaction cai. be precipitated from the resulting solution by strong base to arrive at ari acceptable v.ilver balance.

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COMMERCIAL SOLVE-!TS CORP.

V A

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Report No. Q-9 Page 3

Ratio AICI3 to Reactants

B - 0-3 mole/mole 0 - 0=1 mole/mole;

additional 0.1 mole after £hr. & - 0.1 mole/mole;

additional0.1 mole after 1-3/U hr.

TIME IN HOURS

0.1

+

** - 0.1 mcle/molsj additional 0.1 mole/mole after 3 A hr

O - 0.2 mole/moles additional 0.1 mole after I-3A hr.

2 TiVE !N HOURS

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mmj%

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Report No. Q-9 Page It

It would seem that the conditions of the process for the prepara- tion do have a wide latitxide^ As noted in Table I, there is only slight variation in yield when the salt solution is added as a unit^ added dropwise over a one hour period^ or added and let stand 16 hours befoi-e filtering*. AJLSOJ the yield 'aras not appreciably lowered when no cooling -was used as compared to that when the temperature was not allowed above 30JC. There was however cc=e variation in the ratio of silver precipitated and that re- maining in the reaction solution.

I

r

Dinitropropanediol Preparation(a/

Run TonditioiM

11$ Analytical grade AgNOo; S..P.(C) 116 • " " "

n urn 117

AgNO^ Recovered

Yield(b) from Dake Ra

from ffinate Total

72 iost

57

97.39 96o50 97.33

lo83 2.20 2=20

99.22 98.70 99.53

D^ nitropropanol Prepfir«tion(a;>d)

121 30 "in., ho1 'C

122 S.P . 123 •

I21i(« ) w 126 5 min., 30' 'C 128 18 hours, 30°C 130 S.P „ 132 10 min., 35UC 133 15 min., 13b dropwise "or 1

— 96.9h 2.3U 99.28 82 99.hO .30 99.70 -_. 97.89 1.57 99.U6 — 98,20 1.63 99.83 77 99.71 .52 100.23 87 97.02 2.26 99.28 89 — 1.35 o9 97-02 3.10 100=12 79 — 3-3? — P5 100.28 0..01 100.32

Mean Recovery 99.60

mm<

(a' Runs were made on a 0.50 g-.mole basis (1.0 g. mole AgNOh)-

(b^ Yield -ao based on material extracted but not volatile at 75° and 1-2

'c' S.P. - Standard procedure: Add all of the salt solution to the silver nitrate solution at cr.ce, keep temperature below 30°C, and filtsr after 30 min.

{d) All silver nitrate in this scrie? •*->.z the same r^r-ystaliized, recovered material„

lSJ This run was on a 1.0 g. mole basis.

CONFIDENTIAL

It has been found that DPL has a good solubility differential between ?0°C and room temperature in monochlorotoluene. Better than a 90? yield of nice DPL crystals was obtained from crude product, pulled dry by means of a vacuum pump; using monochlorotoluene and hexane as a mixed re- crystallization solvent.

Table I

I "•-

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COMMERCIAL SOLVHiTS CORP. Report No. Q-9 Page 5

RBPSRENO^

1. C. H. Steapel, R. Cross, and R. Mariella, J. An:. Cham. Soc. J_2, 229? (1950).

2„ T. L. Greshaa, J. Janaen, and F. Shaver, J. Am. Chaw, Soc. (2, 72 (1950).

3. B. F. Goodrich Chemical Co., private comaanication.

U. British Patent 626,772.

5* Cossasrci&l Solvents Reports Q-8, p. 2.

6. D. V. Sickaan, NOL, private communication.

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