#vp; mw

[villapelicanos]

◜» 𝐦 𝐨 𝐬 𝐭  𝐰 𝐚 𝐧 𝐭 𝐞 𝐝

august finch (lucas bravo): procurando familiares que ainda moram na cidade (pode ser primos ou irmãos). obs: a família finch é da cidade, são bem tranquilos e amigáveis.  

august finch (lucas bravo): procurando ex-namorade. obs: teriam namorado quando ele ainda não tinha voltado pra vila. não terminaram muito bem. 

[lurakha]

CALL OF DUTY: MODERN WARFARE II (∞)

[aggravateddurian]

Vega's Halloween Outfit, for when you need to tactically trick or treat at Konpeki Plaza, or if you're becoming the newest Warzone 2077 operator.

She comes in a pack!

For the low, low pricce of 149.99 eurodollars, you too can battle royale as V and Songbird!

[postsofbabel]

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[sorrowfulsoul]

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Contents: Top 0–9 A B C D E F G H I J K L M N O P Q R S T U V W X Y Z

# 0 1 2 3 4 5 6 7 8 9

A Aa Ab Ac Ad Ae Af Ag Ah Ai Aj Ak Al Am An Ao Ap Aq Ar As At Au Av Aw Ax Ay Az

B Ba Bb Bc Bd Be Bf Bg Bh Bi Bj Bk Bl Bm Bn Bo Bp Bq Br Bs Bt Bu Bv Bw Bx By Bz

C Ca Cb Cc Cd Ce Cf Cg Ch Ci Cj Ck Cl Cm Cn Co Cp Cq Cr Cs Ct Cu Cv Cw Cx Cy Cz

D Da Db Dc Dd De Df Dg Dh Di Dj Dk Dl Dm Dn Do Dp Dq Dr Ds Dt Du Dv Dw Dx Dy Dz

E Ea Eb Ec Ed Ee Ef Eg Eh Ei Ej Ek El Em En Eo Ep Eq Er Es Et Eu Ev Ew Ex Ey Ez

F Fa Fb Fc Fd Fe Ff Fg Fh Fi Fj Fk Fl Fm Fn Fo Fp Fq Fr Fs Ft Fu Fv Fw Fx Fy Fz

G Ga Gb Gc Gd Ge Gf Gg Gh Gi Gj Gk Gl Gm Gn Go Gp Gq Gr Gs Gt Gu Gv Gw Gx Gy Gz

H Ha Hb Hc Hd He Hf Hg Hh Hi Hj Hk Hl Hm Hn Ho Hp Hq Hr Hs Ht Hu Hv Hw Hx Hy Hz

I Ia Ib Ic Id Ie If Ig Ih Ii Ij Ik Il Im In Io Ip Iq Ir Is It Iu Iv Iw Ix Iy Iz

J Ja Jb Jc Jd Je Jf Jg Jh Ji Jj Jk Jl Jm Jn Jo Jp Jq Jr Js Jt Ju Jv Jw Jx Jy Jz

K Ka Kb Kc Kd Ke Kf Kg Kh Ki Kj Kk Kl Km Kn Ko Kp Kq Kr Ks Kt Ku Kv Kw Kx Ky Kz

L La Lb Lc Ld Le Lf Lg Lh Li Lj Lk Ll Lm Ln Lo Lp Lq Lr Ls Lt Lu Lv Lw Lx Ly Lz

M Ma Mb Mc Md Me Mf Mg Mh Mi Mj Mk Ml Mm Mn Mo Mp Mq Mr Ms Mt Mu Mv Mw Mx My Mz

N Na Nb Nc Nd Ne Nf Ng Nh Ni Nj Nk Nl Nm Nn No Np Nq Nr Ns Nt Nu Nv Nw Nx Ny Nz

O Oa Ob Oc Od Oe Of Og Oh Oi Oj Ok Ol Om On Oo Op Oq Or Os Ot Ou Ov Ow Ox Oy Oz

P Pa Pb Pc Pd Pe Pf Pg Ph Pi Pj Pk Pl Pm Pn Po Pp Pq Pr Ps Pt Pu Pv Pw Px Py Pz

Q Qa Qb Qc Qd Qe Qf Qg Qh Qi Qj Qk Ql Qm Qn Qo Qp Qq Qr Qs Qt Qu Qv Qw Qx Qy Qz

R Ra Rb Rc Rd Re Rf Rg Rh Ri Rj Rk Rl Rm Rn Ro Rp Rq Rr Rs Rt Ru Rv Rw Rx Ry Rz

S Sa Sb Sc Sd Se Sf Sg Sh Si Sj Sk Sl Sm Sn So Sp Sq Sr Ss St Su Sv Sw Sx Sy Sz

T Ta Tb Tc Td Te Tf Tg Th Ti Tj Tk Tl Tm Tn To Tp Tq Tr Ts Tt Tu Tv Tw Tx Ty Tz

U Ua Ub Uc Ud Ue Uf Ug Uh Ui Uj Uk Ul Um Un Uo Up Uq Ur Us Ut Uu Uv Uw Ux Uy Uz

V Va Vb Vc Vd Ve Vf Vg Vh Vi Vj Vk Vl Vm Vn Vo Vp Vq Vr Vs Vt Vu Vv Vw Vx Vy Vz

W Wa Wb Wc Wd We Wf Wg Wh Wi Wj Wk Wl Wm Wn Wo Wp Wq Wr Ws Wt Wu Wv Ww Wx Wy Wz

X Xa Xb Xc Xd Xe Xf Xg Xh Xi Xj Xk Xl Xm Xn Xo Xp Xq Xr Xs Xt Xu Xv Xw Xx Xy Xz

Y Ya Yb Yc Yd Ye Yf Yg Yh Yi Yj Yk Yl Ym Yn Yo Yp Yq Yr Ys Yt Yu Yv Yw Yx Yy Yz

Z Za Zb Zc Zd Ze Zf Zg Zh Zi Zj Zk Zl Zm Zn Zo Zp Zq Zr Zs Zt Zu Zv Zw Zx Zy Zz

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[agox]

Last night I got high and wrote a program to find all of the unused elemental symbols. It turns out there’s 585 of them and it’s much less interesting the next day.

One interesting finding: I couldn’t be bothered to generate all possible one and two letter strings, so I asked ChatGPT to write me code that would do all that for me. It worked surprisingly well!

['a', 'd', 'e', 'g', 'h', 'j', 'l', 'm', 'q', 'r', 't', 'x', 'z', 'aa', 'ab', 'ad', 'ae', 'af', 'ah', 'ai', 'aj', 'ak', 'an', 'ao', 'ap', 'aq', 'av', 'aw', 'ax', 'ay', 'az', 'bb', 'bc', 'bd', 'bf', 'bg', 'bj', 'bl', 'bm', 'bn', 'bo', 'bp', 'bq', 'bs', 'bt', 'bu', 'bv', 'bw', 'bx', 'by', 'bz', 'cb', 'cc', 'cg', 'ch', 'ci', 'cj', 'ck', 'cp', 'cq', 'ct', 'cv', 'cw', 'cx', 'cy', 'cz', 'da', 'dc', 'dd', 'de', 'df', 'dg', 'dh', 'di', 'dj', 'dk', 'dl', 'dm', 'dn', 'do', 'dp', 'dq', 'dr', 'dt', 'du', 'dv', 'dw', 'dx', 'dz', 'ea', 'eb', 'ec', 'ed', 'ee', 'ef', 'eg', 'eh', 'ei', 'ej', 'ek', 'el', 'em', 'en', 'eo', 'ep', 'eq', 'et', 'ev', 'ew', 'ex', 'ey', 'ez', 'fa', 'fb', 'fc', 'fd', 'ff', 'fg', 'fh', 'fi', 'fj', 'fk', 'fn', 'fo', 'fp', 'fq', 'fs', 'ft', 'fu', 'fv', 'fw', 'fx', 'fy', 'fz', 'gb', 'gc', 'gf', 'gg', 'gh', 'gi', 'gj', 'gk', 'gl', 'gm', 'gn', 'go', 'gp', 'gq', 'gr', 'gs', 'gt', 'gu', 'gv', 'gw', 'gx', 'gy', 'gz', 'ha', 'hb', 'hc', 'hd', 'hh', 'hi', 'hj', 'hk', 'hl', 'hm', 'hn', 'hp', 'hq', 'hr', 'ht', 'hu', 'hv', 'hw', 'hx', 'hy', 'hz', 'ia', 'ib', 'ic', 'id', 'ie', 'if', 'ig', 'ih', 'ii', 'ij', 'ik', 'il', 'im', 'io', 'ip', 'iq', 'is', 'it', 'iu', 'iv', 'iw', 'ix', 'iy', 'iz', 'ja', 'jb', 'jc', 'jd', 'je', 'jf', 'jg', 'jh', 'ji', 'jj', 'jk', 'jl', 'jm', 'jn', 'jo', 'jp', 'jq', 'jr', 'js', 'jt', 'ju', 'jv', 'jw', 'jx', 'jy', 'jz', 'ka', 'kb', 'kc', 'kd', 'ke', 'kf', 'kg', 'kh', 'ki', 'kj', 'kk', 'kl', 'km', 'kn', 'ko', 'kp', 'kq', 'ks', 'kt', 'ku', 'kv', 'kw', 'kx', 'ky', 'kz', 'lb', 'lc', 'ld', 'le', 'lf', 'lg', 'lh', 'lj', 'lk', 'll', 'lm', 'ln', 'lo', 'lp', 'lq', 'ls', 'lt', 'lw', 'lx', 'ly', 'lz', 'ma', 'mb', 'me', 'mf', 'mh', 'mi', 'mj', 'mk', 'ml', 'mm', 'mp', 'mq', 'mr', 'ms', 'mu', 'mv', 'mw', 'mx', 'my', 'mz', 'nc', 'nf', 'ng', 'nj', 'nk', 'nl', 'nm', 'nn', 'nq', 'nr', 'ns', 'nt', 'nu', 'nv', 'nw', 'nx', 'ny', 'nz', 'oa', 'ob', 'oc', 'od', 'oe', 'of', 'oh', 'oi', 'oj', 'ok', 'ol', 'om', 'on', 'oo', 'op', 'oq', 'or', 'ot', 'ou', 'ov', 'ow', 'ox', 'oy', 'oz', 'pc', 'pe', 'pf', 'pg', 'ph', 'pi', 'pj', 'pk', 'pl', 'pn', 'pp', 'pq', 'ps', 'pv', 'pw', 'px', 'py', 'pz', 'qa', 'qb', 'qc', 'qd', 'qe', 'qf', 'qg', 'qh', 'qi', 'qj', 'qk', 'ql', 'qm', 'qn', 'qo', 'qp', 'qq', 'qr', 'qs', 'qt', 'qu', 'qv', 'qw', 'qx', 'qy', 'qz', 'rc', 'rd', 'ri', 'rj', 'rk', 'rl', 'rm', 'ro', 'rp', 'rq', 'rr', 'rs', 'rt', 'rv', 'rw', 'rx', 'ry', 'rz', 'sa', 'sd', 'sf', 'sh', 'sj', 'sk', 'sl', 'so', 'sp', 'sq', 'ss', 'st', 'su', 'sv', 'sw', 'sx', 'sy', 'sz', 'td', 'tf', 'tg', 'tj', 'tk', 'tn', 'to', 'tp', 'tq', 'tr', 'tt', 'tu', 'tv', 'tw', 'tx', 'ty', 'tz', 'ua', 'ub', 'uc', 'ud', 'ue', 'uf', 'ug', 'uh', 'ui', 'uj', 'uk', 'ul', 'um', 'un', 'uo', 'up', 'uq', 'ur', 'us', 'ut', 'uu', 'uv', 'uw', 'ux', 'uy', 'uz', 'va', 'vb', 'vc', 'vd', 've', 'vf', 'vg', 'vh', 'vi', 'vj', 'vk', 'vl', 'vm', 'vn', 'vo', 'vp', 'vq', 'vr', 'vs', 'vt', 'vu', 'vv', 'vw', 'vx', 'vy', 'vz', 'wa', 'wb', 'wc', 'wd', 'we', 'wf', 'wg', 'wh', 'wi', 'wj', 'wk', 'wl', 'wm', 'wn', 'wo', 'wp', 'wq', 'wr', 'ws', 'wt', 'wu', 'wv', 'ww', 'wx', 'wy', 'wz', 'xa', 'xb', 'xc', 'xd', 'xf', 'xg', 'xh', 'xi', 'xj', 'xk', 'xl', 'xm', 'xn', 'xo', 'xp', 'xq', 'xr', 'xs', 'xt', 'xu', 'xv', 'xw', 'xx', 'xy', 'xz', 'ya', 'yc', 'yd', 'ye', 'yf', 'yg', 'yh', 'yi', 'yj', 'yk', 'yl', 'ym', 'yn', 'yo', 'yp', 'yq', 'yr', 'ys', 'yt', 'yu', 'yv', 'yw', 'yx', 'yy', 'yz', 'za', 'zb', 'zc', 'zd', 'ze', 'zf', 'zg', 'zh', 'zi', 'zj', 'zk', 'zl', 'zm', 'zo', 'zp', 'zq', 'zs', 'zt', 'zu', 'zv', 'zw', 'zx', 'zy', 'zz']

[romilly-jay]

COSY CATASTROPHE: Cosiness observed in The Martian

The Martian – Andy Weir. The Martian has been described as “only barely” science fiction, in that it’s set c. 50 years into the future, using close iterations of extant technology.

The story began as Andy Weir’s thought experiment, published online initially, examining how close we are to being able to survive on Mars using recognisable existing technologies.

Basically AW came up with a series of problems or threats and inflicted them one after another on his hapless protagonist, then tried to deal with the problem so that the protagonist survived.

Despite the apparently extreme survival context, I rank this book as mostly cosy and that’s directly because the VP character, MW, is almost unremittingly cheerful despite facing a one-man extinction-level event (no-one else is facing catastrophe but he also represents 100% of the human population on Mars so technically…).

MW puts his faith in science and science does not let him down.(Occasionally, he lets science down, but luckily for him, not fatally.)

MW also puts full faith in his crewmates, who he clearly considers as friends and they also do not let him down. He goes to lengths not to blame them for the initial marooning and when it comes to the decision moment for them, they - of course - make the brave choice.

===============================================

Staying with Andy Weir, Project Hail Mary feels (to me) like it’s essentially the same protagonist but this time in a much more extreme SF context and with some real flaws. The result is a somewhat less cosy narrative - and certainly to begin with.

This time, an amnesia situation, where the narrative takes place both in the present (in space) and in the past (as the character remembers things). There are character flaws to be overcome, but as before, the big enemy is the natural environment.

In the hands of another writer, this plot would not be cosy AT ALL but AW reverts to science enthusiasm, alien encounter enthusiasm, problem-solving enthusiasm, and huge enthusiasm for friendship.

I'm here for all this. It's a tone that works really well for this reader.

[paikesolutions]

NHPC Takes Flight: Analyzing the 161% Stock Surge and What Lies Ahead

NHPC, India's premier hydropower producer, has taken the stock market by storm, soaring a staggering 161% from its 52-week low and becoming a true market darling. This remarkable climb has left both investors and analysts scratching their heads, eager to understand the driving forces behind this phenomenal rise and predict the company's future trajectory. This article delves deep into the factors propelling NHPC's ascent, examines potential concerns, and explores the diverse opinions of experts to provide a comprehensive perspective on this intriguing market phenomenon.

Fueling the Flame: Key Catalysts for the Upward Surge

Several key factors have contributed to NHPC's impressive stock performance:

1. Riding the Green Energy Wave: The Indian government's ambitious goals for renewable energy transition have put a spotlight on clean power sources like hydropower. NHPC, with its established hydroelectric infrastructure and expertise, stands well-positioned to capitalize on this growing demand, making it an attractive proposition for investors looking to tap into the green energy boom.

2. A Project Launch with a Spark: The recent announcement of a 300 MW solar power project in collaboration with the government, backed by a substantial investment of over Rs 1,732 crore, further bolstered investor confidence. This strategic move demonstrates NHPC's commitment to diversifying its renewable energy portfolio and aligns with the national green agenda, solidifying its image as a key player in the clean energy transformation.

3. Analyst Cheerleading Squad: Many analysts have sung NHPC's praises, offering bullish price targets ranging from Rs 105 to 135, with strong support zones identified around Rs 80-88. This positive sentiment adds fuel to the fire, attracting more investors looking to benefit from the predicted upward trajectory.

4. Technical Tailwinds: From a technical standpoint, the momentum seems favorable. The Relative Strength Index (RSI) sits comfortably below the overbought zone, indicating room for further growth. Additionally, trading above key moving averages further underscores the stock's bullish sentiment.

However, Cautionary Flags Need Heeding

While the current scenario appears rosy, it's crucial to acknowledge potential concerns that could impact NHPC's future performance:

1. Q3 Earnings Woes: The company's recent Q3 earnings revealed a decline in both net profit and revenue compared to the previous year. This raises questions about its immediate financial health and raises concerns about its ability to sustain its impressive growth in the long run.

2. Industry Valuation Comparison: NHPC's current valuation seems stretched compared to its peers in the sector. With a P/E ratio of 26.03, it sits slightly above the industry average of 24.89. This could indicate a potential overvaluation risk, making some investors apprehensive.

3. Short-Term Consolidation on the Horizon?: Although bullish overall, some analysts predict a period of consolidation following the sharp rally. This could lead to short-term volatility, potentially unnerving investors with shorter time horizons.

Expert Opinions: A Spectrum of Perspectives

Analysts and market experts offer diverse views on NHPC's future:

Bullish Outlook:

"The stock holds significant upside potential with positive momentum and government support for green energy," says Shiju Koothupalakkal, Technical Research Analyst at Prabhudas Lilladher.

"NHPC's strong technicals and alignment with national green goals make it a compelling investment," adds KKunal V Parar, VP of Technical Research at Choice Broking.

Cautious Optimism:

"While the long-term trend appears positive, a short-term consolidation is likely before further upward movement," suggests Ruchit Jain, Lead Research at 5paisa.com.

Balancing Act for Investors:

NHPC's current situation presents a complex scenario for investors. The undeniable growth potential fueled by renewable energy initiatives and analyst confidence is countered by valuation concerns and recent earnings decline. The decision to invest ultimately hinges on individual risk tolerance and investment horizon.

Conclusion: Navigating the NHPC Journey

NHPC's remarkable stock surge has captured market attention, but a balanced approach is crucial before making investment decisions. Understanding the driving forces, both positive and negative, and carefully considering expert opinions are essential steps towards navigating this dynamic situation. As the company continues its journey in the evolving energy landscape, staying informed and conducting thorough research will be key for investors seeking to seize potential opportunities while mitigating risks.

[semiconducting]

i like my oc aesthetic tags :~)

[villapelicanos]

◜» 𝐦 𝐨 𝐬 𝐭  𝐰 𝐚 𝐧 𝐭 𝐞 𝐝

prudence lucas (zoey deutch): procurando o irmão mais novo de 20 anos até 25. 

hange serafin (taylor perez): procurando colegas de banda (qualquer instrumento). 

hyuk min-ho (kim min kyu): procurando mãe do filho dele de 7 anos (qualquer idade). 

yeager ackerman (ben robson): procurando irmãos mais novos e mais velhos, adotados ou não (qualquer idade). 

angelo kroos (jacob elordi): procurando rolo vai e volta e que nunca realmente namora.

[lurakha]

CALL OF DUTY: MODERN WARFARE II (∞)

[moonliightsx]

@xscpphirehq​

The days flew as Aryan and Mahi were caught up in their own bliss. Working became difficult simply because all he wanted to do was to flirt and banter with his girlfriend, who was learning everything rapidly. It had been close to five months now since she first joined MW and she’d made him proud at every turn. Gaurav too had noted it and came by one day to see how they were doing and once Aryan filled him in all that Mahi had learned and done so far, he could see the pride shining in the old man’s gaze for his daughter. In the meantime, she had also spent more time with Papa, and the VP was so happy to see the father-daughter bonding. They had just come out from a meeting and normally they go back to work, after a little more flirting, but today, Papa had showed up at the office so Aryan held himself from leering at his girlfriend in front of her father. Gaurav wanted to have lunch with the couple, but it appeared he had made himself busy while they were in a meeting. Aryan caught another woman with him, a rather attractive one and it looked like Papa was almost flirting with the women. The VP turned to Mahi with an amused look, “it looks you dad is smitten with someone. Look.” He gestured to the pair, chatting and the way Gaurav was smiling. “Do you know her?”

[postsofbabel]

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[juniperpublishersajop]

A New Composition of High Heat General Purpose Polystyrene (High Heat GPPS) Resin

Abstract

A new composition of high heat general-purpose polystyrene (High heat GPPS) resin synthesis is discussed. The new composition of resin involves addition of cross-linker/comonomer in very low concentration during synthesis process. Commercially available vinyl cross-linkers like divinylbenzene (DVB), Ethylene dimethacrylate (EDM), Tricycle (5.2.1.02,6) decanedimethanol diacrylate (TDDDA), Dicyclopentadiene (DCPD) and vinyl comonomer like maleic anhydride, α-methylstyrene have been evaluated via bulk polymerization method. DVB showed enhancement in the heat distortion temperature (HDT), vicat softening temperature (VST) & melt flow index (MFI) compared to the benchmark grade of GPPS, whereas other mechanical and impact properties remained same or better than benchmark grade under identical methods of measurement.

Keywords: Divinylbenzene; Cross-linked; Branching; Polymerization; Heat Distortion Temperature (HDT); Melt Flow Index (MFI)

Abbreviations: HDT: Heat Distortion Temperature; MFI: Melt Flow Index; DVB: Divinylbenzene; EDM: Ethylene Dimethacrylate; TDDDA: Tricycle (5.2.1.02,6) Decanedimethanol Diacrylate; DCPD: Dicyclopentadiene; VST: Vicat Softening Temperature; High Heat GPPS: High Heat General- Purpose Polystyrene

Introduction

Polystyrene (PS) is a multipurpose polymer used in varied applications in rigid and foamed forms. Based on orientation of phenyl group on the polymer backbone, polystyrene can be classified into isotactic, syndiotactic and atactic. Isotactic or syndiotactic polystyrene prepared by metallocene catalyst can give HDT/VST around 250 oC and shows lowest specific gravity compared to any other engineering plastics in the market [1]. XAREC is world’s first syndiotactic polystyrene commercialized by Idemitsu Corporation, used in electronic component molding [2]. The first two are commercially not important due to complexity in the synthesis and processability compared to atactic polystyrene. Atactic polystyrene is known as generalpurpose polystyrene (GPPS). It is produced by simple thermal initiated radical bulk polymerization [3]. GPPS is clear, hard and can be used in packaging, household items, and electronics. The excellent physical and processing properties make GPPS suitable for many applications as compared to any other plastics, but its glass transition temperature (Tg) is only 100 oC that leads to limit its use in certain applications. Tg dictates the continuous service temperature that is a very important factor for polymer to evaluate its processing and application performance. Therefore, there is a demand for high Tg GPPS. Some efforts have been reported in this direction by copolymerizing styrene with maleimide and imide, which act as hydrogen-bond interaction site in the copolymer [4]. Although there is no direct relation between Tg and HDT in polymers, but in amorphous polymer like GPPS, HDT is close to Tg [5].

HDT can be improved by increasing the interaction of chains or by restricting the chain mobility at elevated temperature. Although GPPS synthesis process is well established and matured, the market requirement and customer application always demand to develop new process or improve the efficiency of the process. Vinyl based anhydrides, amides, maleimides and methylstyrenes have been explored as comonomers in different loading to enhance the heat resistance of polystyrene [4-5]. This is generally achieved by introducing heteroatom containing monomer in the polystyrene chain, which leads chemical irregularity or steric hindrance in the polystyrene chain. GPPS has been widely used in food packaging containers, disposable containers, kitchenware & cutleries owing to its excellent transparency, water resistance and colorability. Molded articles prepared by GPPS with lower HDT/VST can undergo structural deformation especially when they are used in hot filled applications and lower HDT can affect the production rate during molding due to the long cycle time. Good thermal properties like higher HDT/VST along with flow are important requirement for the product performance with better heat stability & shorter cycle time in the production line. Therefore, our research was focused in first instant to increase the Tg and HDT/VST, without affecting flow properties.

Experimental Section

Material and Methods

All the chemicals that were used in the process procured from Sigma-Aldrich and used as such.

Gel-permeation chromatography (GPC)

The molecular weight of intermediate samples and final polymer was measured by GPC at 40 oC (Make-Shimadzu, Class-VP). THF was used as mobile and diluent solvent, sample concentration 2 mg/ml, column specification- PLgel 5 μm MIXED-C, 300 x 7.5 mm, Detector- UV @254nm, standards- Monodispersed polystyrene standards.

Differential scanning calorimetry (DSC)

Differential scanning calorimetry (DSC) of the samples was done with TA Instruments/DSC Q 1000 by heating the samples from room temperature to 160 ºC and heating rate always maintained at 10 ºC/min in nitrogen atmosphere.

High performance liquid chromatography (HPLC)

Unreacted residual styrene monomer was detected and quantified by high performance liquid chromatography (HPLC) Agilent HPLC-1260 series. The chromatographic condition are as follows, column- Agilent Zorbax,-C18, (4.6X150mm), 5μ; Mobile phase: Reservoir A -0.02% Orth phosphoric acid in Milli-Q water, Reservoir B-Methanol, Reservoir C - Acetonitrile at different gradients. Flow rate 1 ml/min, detector-diode array detector, wave lenth-254 nm. Column temperatue-40 oC.

Melt flow index (MFI)

Melt flow index was measured at 230 oC & 2.16 kg load as per the ASTM D 1238, in GOTTFERT MFI machine (model-MI-4).

Heat distortion temperature (HDT)

Heat distortion temperature was measured as per the ASTM D648, method B at 0.45 MPa load, on the CEAST machine. All the samples were annealed for 70 hrs. at 70 oC prior to test.

Vicat softening temperature (VST)

Vicat softening temperature was also measured in CEAST machine for annealed samples as per ASTM D1525. All the samples were annealed for 70 hrs. at 70 oC prior to test.

Mechanical property (Tensile and Izod Impact notched)

Injection molded specimens are conditioned for 48 h at 23 oC & relative humidity at 50%. Tensile strength was measured were accordance to ASTM D638, on Zwick 2.5 RTI-UTM machine. Izod impact notched was measured as per the ASTM D256.

Polymerization and Processing

Comonomer/cross linker screening

The following comonomers/cross linkers were screened in 100 g batch scale, the concentration of comonomer was maintained at 0-5 wt. %.

Styrene with comonomer was transferred to the pre-heated (128 oC) glass reactor, the residence time/reaction time and temperature were increased at four different time intervals to make a continuous process. Intermediate samples were collected to monitor molecular weight, Tg and conversions at every 1 h interval. Unreacted styrene monomer or residual monomer was removed by precipitating polymer solution (in THF) in hexane and then measured Tg.

Scale-up (1kg) in lab glass reactor setup

Following three formulation were shortlisted for scale-up in 1kg scale in the lab glass reactor setup (Figure 1 SI) based on the screening experimental results and evaluated thermal, flow & mechanical properties. The reaction conditions were kept as in Table 1. The unreacted styrene was removed by applying high vacuum (0-30 mbar) for 10-12 min at the end of the polymerization.

a. High molecular weight GPPS (Mw > 300 kg mol-1)

b. Evaluation of cross linker DVB at 100 ppm loading

c. Evaluation of comonomer MA at 5 wt. % loading

GPPS process and compounding

To evaluate the final properties of the synthesized polystyrene and copolymers were processed in different steps as shown in the Figure 1.

Results and Discussion

Different approaches to develop high heat GPPS

Based on literature search and our expertise three different approaches had been identified to achieve the targeted properties (CTQ’s).

a. High molecular weight GPPS (Mw > 300 kg mol-1)

b. Evaluation of cross linkers & comonomers

High molecular weight GPPS (Mw >300 kg mol-1)

This approach is simple and straightforward; this has been achieved by optimizing reaction time and temperature of the synthesis process as shown in the Table 2. In general, polystyrene molecular weight (Mw) can grow up to 340-350 kg mol-1 in radical bulk polymerization technique at 3-3.5 h reaction time (pre-poly), but later decreased due to thermal degradation and long residential time. In order to achieve Mw ≥300 kg mol-1, the polymerization was stopped after 4 h reaction time, with ~ 80 % conversion. At final stage high vacuum was applied for 10 min to remove 17-18 % unreacted styrene, after double extrusion the final residual was 1500 ppm.

From Table 3, MFI data shows that as molecular weight increased the flow decreased, but HDT and VST increased by 2 oC. Other mechanical properties like impact and tensile properties are better or equal to the baseline material PS160. Due to the low MFI, high molecular weight approach may have negative effect on processability and cycle time during molding. Figure 2, the GPC chromatograms shows that decreased molecular weight due to thermal degradation at different stages of processing.

Evaluation of cross linkers & comonomers

Following cross linkers and comonomers were screened at different loading for high heat GPPS (Table 4) at 100 g scale. All the cross linkers were screened in the range of 50-500 ppm to avoid gelling in the reactor, whereas comonomers were tested in 1-5 wt. % loading. DVB was shortlisted for scale-up in 1kg scale and evaluated for thermal and mechanical properties as it showed better Tg (107 oC, when residual styrene ~100 ppm). Moreover, it is commercially available in bulk quantities, FDA approved and reactivity is almost similar to the styrene monomer [6-7]. The same formulation was scaled up to 5 kg scale in batch reactor in similar reaction conditions. Tricyclo (5.2.1.02,6) decane dimethanol diacrylate and N,N-Hexamethylenebis (methacrylamide) as crosslinkers did not show any improvement in Tg in the final polymer. MA showed best Tg among comonomers at 4-5 wt. % loading and was scaled up to 1 kg in lab scale. DVB loading was optimized to 100 ppm, higher loading showed low MFI (< 3.0 g/10 min) because of high molecular weight and more crosslinking. Intermediate sample analysis showed that molecular weight increased up to 3rd hour and then started decreasing (Figure 3). This is may be due to thermal degradation under dynamic reaction conditions. Styrene-DVB copolymer always gave broader PDI (≥3.0) due to partial crosslinking or chain extension/branching, which leads to higher MFI. The chain extension was envisaged by lower slope/slower relaxation in the lower frequency region in rotational rheometer study as shown in Figure 4.

Solid content and viscosity at prepoly stage was almost similar to the homopolymer (Table 5). From Figure 7 it is very clear that residual styrene can affect Tg, that is higher the residual, lower the Tg, hence HDT/VST can also change accordingly (Table 6). It is required to maintain optimum level of (< 500 ppm, more preferably < 200 ppm as in example 2) residual in the final polymer to hit HDT > 102 oC or VST >106 oC as showed in table 6, example 2-4. The mechanical properties as if tensile strength & impact were better than the baseline PS160 (Table 6). There is no change in the thermal stability of styrene-DVB copolymer at 100 ppm DVB loading in compared to baseline GPPS PS160 (Figure 2 SI). Comonomers were evaluated in 1-5wt.% loading along with styrene, under similar reaction conditions as mentioned in the Table 2. Maleic anhydride (MA) showed HDT-102 oC, and MFI ~ 10-12 at 5 wt. % loading, but imparts haziness to the final polymer and more brittle than baseline PS 160. MA cannot homopolymerize, however in the presence of styrene it always forms alternative copolymer. This is may be due to higher activity of MA (0.02 time higher than styrene) [8].

Since, we are restricted ourselves to MA content to 5 wt. % maximum in the formulation, MA was added slowly over 1 h time in the prepoly stage and anticipated fair distribution throughout the chain. As MA content increased in the formulation the copolymer molecular weight decreased below critical molecular weight (~240 kg mol-1) as showed in the Table 7 & Figure 9. As 5 wt. % loading showed Tg~ 108 oC (Figure 10), the same was scaled up to 1kg in the lab reactor and evaluated for the mechanical and thermal properties. In styrene-MA copolymerization, the propagating chains were styrinic in nature because the maleic anhydride radicals undergo chain transfer reaction in this highly reactive system [9]. The styrene-MA system was highly exothermic compared to styrene homopolymerization and styrene-DVB system. This is because hydrogen abstraction from the maleic anhydride radical is 40 kJ/ mol more exothermic than that of styrene radical. This finally leads to inferior mechanical properties compared to the baseline as shown in the Table 7. Other comonomers like alpha-methylstyrene and DCPD did not show considerable improvement in thermal or flow properties up to 5 wt. % loading.

Conclusion

Divinylbenzene (DVB) as a crossliker at 100 ppm loading showed balance of thermal and flow properties as compared to baseline PS160. The controlled crosslinking of polystyrene chains by DVB play major role in broad distribution of molecular weight and hence better flow (MFI). There is an increment in the HDT/ VST by 2-3 oC and MFI from 3.3 g/10 min to 7 g/10 min without compromising any other properties of GPPS.

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[hiddenwashington]

[LEIA ORGANA || WILLA HOLLAND] is awaiting the arrival of their [VICE PRESIDENT]. If you happen to see them, they are around [25+] years old and look strikingly similar to [UTP] and happen to be from [UTP]. If you see them, you [DO] have to contact them. We hope they find them soon. [for real this could be a canon/an oc, i’m not picky about female/male any fcs, just come hmu to let me know they’re coming in. they can get along, can hate each other, anything!! i’m up for anything and everything].

( +1 ) wanted connection added !