Gukorana kwa Diluents zivura UV (Free-Radical UV Diluents)

Uburyo bwo gukora acrylate reactive diluents burimo cyane cyane esterification igororotse, transesterification, aside chloride method, phase-transfer catalysis, na addition esterification. Ariko, inyinshi muri zo zikorwa hifashishijwe esterification igororotse.

(1) Gupima neza imiterere y'izuba (esterification) mu buryo butaziguye

CH₂ = CHCOOH + ROH -umusemburo → CH₂ = CHCOOR + H₂O

  Katalysts zikoreshwa cyane mu gupima neza ibintu birimo aside sulfuriki, aside p-toluenesulfonike, na aside methanesulfonike. Gukoresha aside sulfuriki ikomeye nk'umuti ugabanya ubushyuhe akenshi bitera ingaruka mbi nko kubura amazi, oxidation, no kwipima ubwabyo. Ibi bitanga umusaruro utandukanye, bikagora gutunganya ibicuruzwa no kugarura ibikoresho fatizo, bikabangamira inzira zo kuvurwa, kandi bikangiza ubwiza bw'ibicuruzwa mu gihe bingiza ibikoresho. Kubera iyo mpamvu, PTSA ikoreshwa cyane mu nganda zigezweho kubera ibyiza byayo, harimo ibisabwa bike, ubushyuhe buke bwo gupima, igipimo cyo guhindura ibintu, n'ubwiza bw'ibicuruzwa. Iyo birangiye, katalysts zishobora gutandukanywa byoroshye n'ibicuruzwa, byoroshya imikorere y'ibikorwa. Amazi akorwa mu gihe cyo gupima amazi akurwaho hakoreshejwe imashini igabanya amazi mu mazi (azeotropic entrainer). Imashini zikunze gukoreshwa harimo benzene, toluene, xylene, cyclohexane, na n-heptane, zikora azeotropes hamwe n'amazi yo kuyitwara. Alkanes zirahenze kandi zirahindagurika cyane; xylene ifite aho ishyuha cyane; benzene ifite aho ishyuha hasi kandi ihindagurika cyane, bigatuma bigorana gukira, kandi igaragaza uburozi bwinshi. Kubwibyo, toluene muri rusange ikundwa nk'imashini ishyuha. Toluene ifite aho ishyuha 110°C n'aho ishyuha azeotropic mu mazi ifite aho ishyuha 84°C; irakomera byoroshye mu gihe cyo gukuraho solvent mu cyuma gishyuha, bigatuma ikira neza, uburozi buke ugereranyije na benzene, kandi ikaba ihendutse cyane. Ariko, mu myaka ya vuba aha, amategeko agenga solvents za benzene mu bipfuka, wino, na kole byatumye abakora benshi bareka toluene bagahitamo imashini zikoresha alkane. Ibikoresho bibuza polimeri bigomba gushyirwaho mu gihe cyo gupima kugira ngo hirindwe ko monomer ya aside acrylic itangira gukora polimeri mbere y’igihe ndetse n’umusaruro wa acrylate uvamo. Ibikoresho bikunze gukoreshwa birimo ibinyabutabire bya phenolic (nka hydroquinone [HQ] na tert-butylhydroquinone [TBHQ]), ibinyabutabire bya amine (nka phenothiazine na p-phenylenediamine), hamwe n’ibinyabutabire byo guhuza umuringa (nka dimethyldiethyldithiocarbamate na dibutyl dithiocarbamate), bikoreshwa ukwabyo cyangwa nk’uburyo buvanze. Ku bijyanye n’ubushyuhe bwinshi bwa alkyl acrylates, hashobora gukoreshwa uburyo bwo gupima ubushyuhe bwa melt esterification. Ubu buryo bukuraho gukenera entrainer kandi bukagabanya ingano isabwa ya catalysts na inhibitors. Nyuma yo kugira reflux reaction kuri 110–120°C, amazi aragabanuka, maze aside acrylic idakora neza n’amazi asigaye bigakurwamo binyuze mu gusya mu cyuma, bigatuma alkyl acrylates nyinshi zifite ubuziranenge bwinshi n’umusaruro mwinshi.

(2) Guhindura imiterere y'ibimera mu buryo bwa transsester

CH₂=CHCOOCH₃ + ROH → CH₂=CHCOOR + CH₃OH

  Mu gihe cyo gutegura akrilati nyinshi cyangwa akrilati zikora binyuze mu guhindura imiterere y’ibinyabutabire, akrilati ya methyl ikunze gutorwa nk'ibikoresho byo gutangira bya akrilati zo hasi. Bitewe n'uko ubushyuhe bwayo buke (80°C), esterifiza igomba gukorwa ku bushyuhe buke, bigatuma igihe cyo gukora inyito kiyongera. Byongeye kandi, methanol ikomoka ku binyabutabire ikora azeotrope ifite akrilati ya methyl (ubushyuhe buri hagati ya 62–63°C), itwara akrilati ya methyl ikora inyito bityo ikagabanya umusaruro wa ekarilati nyinshi. Akrilati ya methyl n'akrilati nyinshi zikunze kwibasirwa cyane na copolymerization na homopolymerization, birushaho kugabanya umusaruro wa akrilati nyinshi; bityo, ubwiyongere bw'ibipimo bya inhibitors bukunze gukenerwa. Bitewe n'ibiciro n'ingorane nyuma yo kuvurwa, ubu buryo ntibukikoreshwa mu bucuruzi mu gukora akrilati nyinshi za akrilati na akrilati zikora.

(3) Uburyo bwa aside chloride

CH₂ = CHCOOH + SOCl₂ → CH₂ = CHCOCl + HCl + CO₂

CH₂=CHCOCl + ROH → CH₂=CHCOOR + HCl

  Ubu buryo bubanza gukorana na aside acrylic na thionyl chloride kugira ngo bukore acryloyl chloride, hanyuma igakora esterification reaction hamwe na alcohol. Nta catalysts cyangwa entrains zisaba. Kubera ko reaction ibaho ku bushyuhe buke, kongeramo imiti ibuza polymerization nabyo birindwa. Esterification ibaho hafi mu bwinshi, igatanga ubuziranenge budasanzwe bw'umusaruro. Ariko, ni inzira y'intambwe ebyiri ifite ibiciro biri hejuru by'umusaruro. Reaction ikora ingano nini ya HCl na SO₂ gaze, isaba sisitemu zo gukaraba mu byiciro byinshi hamwe na alkaline ivanze n'amazi kugira ngo inyurwe.

(4) Ingano yo Guhindura Ingano (PTC)

2CH₂ = CH₃ | C-COOH + Na₂CO₃ → 2CH₂ = CH₃ | C-COONa + CO₂ + H₂O

CH₂ = CH₃ | C-COONa + ClCH₂-CH₂O → CH₂ = CH₃ | C-COOCH₂-CH₂O + NaCl

  Methacrylate ya sodium ibaho nk'ikintu gikomeye, mu gihe epichlorohydrine ari amazi. Iyo nta catalyst ihari, imikorere hagati yazo iragenda buhoro cyane, bikaba ngombwa ko hakoreshwa catalyst yo kohereza ibice (PTC). Catalyst zikwiye zo kohereza ibice zirimo umunyu wa ammonium wa quaternary, umunyu wa fosfonium wa quaternary, na ethers. Umunyu wa ammonium wa quaternary ni wo ukunze kugaragara cyane, nka cetyltrimethylammonium chloride (CTAC), benzyltrimethylammonium chloride (BTMAC), na tetramethylammonium chloride (TMAC). Kuba hari ubushuhe mu buryo bw'imyitozo bitera ingaruka mbi; bityo rero, kugira ngo umusaruro urusheho kuba mwiza, ibikoresho fatizo ndetse n'uburyo bw'imyitozo bigomba kugumana amazi gusa kandi byumye.

(5) Kongeramo Esterification

CH₂=R₁|C-COOH + CH₂-CH₂O-R₂ → CH₂=R₁|C-COO-CH₂-OH|CH₂-R₂

  Mu kwinjiza ethylene oxide cyangwa propylene oxide mu buryo butaziguye (meth) aside acrylic mu gihe hari catalyst, habaho esterification yo kongeramo impeta, ikora hydroxy (meth) acrylates (nka HEA, HEMA, HPA, cyangwa HPMA).