CS252738B1 - Method of unsaturated organic acids',their esters' and anhydrides' polymers and copolymers netting - Google Patents
Method of unsaturated organic acids',their esters' and anhydrides' polymers and copolymers netting Download PDFInfo
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- CS252738B1 CS252738B1 CS856667A CS666785A CS252738B1 CS 252738 B1 CS252738 B1 CS 252738B1 CS 856667 A CS856667 A CS 856667A CS 666785 A CS666785 A CS 666785A CS 252738 B1 CS252738 B1 CS 252738B1
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- 229920000642 polymer Polymers 0.000 title claims description 38
- 229920001577 copolymer Polymers 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 12
- 150000002148 esters Chemical class 0.000 title claims description 6
- 150000008064 anhydrides Chemical class 0.000 title claims description 4
- 150000007524 organic acids Chemical class 0.000 title claims description 4
- 235000005985 organic acids Nutrition 0.000 title claims description 4
- 238000004132 cross linking Methods 0.000 claims description 16
- 229920001281 polyalkylene Polymers 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- 241000605112 Scapanulus oweni Species 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000000499 gel Substances 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004577 thatch Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 acrylate ester Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 229940116336 glycol dimethacrylate Drugs 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Doteraz známe postupy sietovania polymérov, alebo kopolymérov esterov kyseliny akrylové), alebo kyseliny metakrylovej sú založené predovšetkým na kopolymerizácii s divinylovými monomérmi. Pri výrobě polymetylmetakrylátových dosiek so zvýšenou tvrdosťou a tepelnou odolnosťou sa pri polymerizácii metylmetakrylátu přidává do· systému glykoldimetakrylát, ktorý zosietuje jednotlivé makromolekulové reťazce, čo prinása zlepšenie úžitkových vlastností polyméru [P. Hayden, H„ W. Melville: J. Polymer Sci. 43, 141, 240 (1960)].The prior art processes for crosslinking polymers or copolymers of esters of acrylic acid) or methacrylic acid are based primarily on copolymerization with divinyl monomers. In the manufacture of polymethyl methacrylate sheets with increased hardness and heat resistance, the polymerization of methyl methacrylate is added to the glycoldimethacrylate system, which crosslinks the individual macromolecular chains, thus improving the performance of the polymer [P. Hayden, H. W. Melville: J. Polymer Sci. 43, 141, 240 (1960)].
Zosietený polymér má na druhej straně natoíko zhoršené tokové vlastnosti taveniny, že sa nedá využit pre spracovanie technológiou tvarovania výrobkov z taveniny polyméru, ani technológia tvarovania v plastickej konzistencii polymeru. Syntéza polymérnych sietí týmto sposobom je významná například pri príprave hydrogélov, sorbentov a podobné.The crosslinked polymer, on the other hand, has a deteriorated melt flow properties such that it cannot be used for processing by the polymer melt article molding technology or by the plastic-like polymer molding technology. The synthesis of polymeric networks in this manner is important, for example, in the preparation of hydrogels, sorbents and the like.
Ďalšia možnost uskutočnenia sietovania termoplastických polymérov na báze akry2 látových monomérov spočívá v dvojstupňové) polymerizácii. Monomér obsahujúci dve dvojité vazby s rozdielnou reaktivitou sa najskór kopolymerizuje s akrylátovým esterom, pričom zreaguje jedna vlnylová skupina. Druhá dvojitá vazba zreaguje pri sletovaní polyméru [Ρ. M. J. Koch de Gooreynd: C. 7 312 (1958)]. Iný podobný postup využívá ako sieťujúce činidlo metakrolein. Vinylová skupina reaguje pri polymerizácii radikálovým mechanizmom a karbonylová skupina umožňuje zosietenie kondenzačnými reakciami [R. C. Schulz W. Passmann: Makromol. Chem. 72, 198 (1964)].Another possibility of carrying out the crosslinking of the thermoplastic polymers based on acrylic monomers consists in a two-stage polymerization. A monomer containing two double bonds of different reactivity is first copolymerized with an acrylate ester, reacting one wave group. The second double bond reacts when the polymer is fused [Ρ. Koch de Gooreynd, M.J., C. 7 312 (1958)]. Another similar procedure uses metacrolein as a crosslinking agent. The vinyl group reacts during polymerization by a radical mechanism and the carbonyl group allows crosslinking by condensation reactions [R. C. Schulz W. Passmann: Macromol. Chem. 72, 198 (1964)].
Bol opísaný aj postup dodatočného sieťovania polymérov a kopolymérov vyšších esterov kyseliny metakrylovej peroxidmi [J. Bartoň: J. Polymer Sci. A—1, 6, 1 315 (1968) ]. Avšak perexidické sieťovanie podobné ako aj sieťovanie radiačně nie je pre polyakryláty, alebo polymetakryláty výhodné, pretože tieto polyméry vplyvom peroxidov a žiarenia majú zvýšený sklon k degradácii [A. ChapirO': Radiation chemistry of polymeric systems, J. Wiley and Sons Intersci. Publ., NY, London, 509 až 525 (1962)].A procedure for post-crosslinking polymers and copolymers of higher methacrylic acid esters with peroxides has also been described [J. Barton: J. Polymer Sci. A-1, 6, 1315 (1968)]. However, perexide crosslinking, like radiation crosslinking, is not preferred for polyacrylates or polymethacrylates, since these polymers have an increased tendency to degrade due to peroxides and radiation [A. Chapir®: Radiation chemistry of polymeric systems, J. Wiley and Sons Intersci. Publ., NY, London, 509-525 (1962)].
Sieťovanie už připravených polymérov akrylátového typu sa dosahuje aj tým, že alkoholový radikál esteru obsahuje reaktivně skupiny, napr. epoxidové [A. Berlin: Vyso252738 komol. Sojed. 1, 962 (1959)]. Tieto skupiny reagujú pri zvýšenej teplote navzájom, alebo s inými vhodnými viacfunkčnými činidlami, ako sú napr. fenolformaldehydové resoly, čím vyvolajú zosietenie makromolekúl akrylátového polymérú [P. F. Sanders: C. 7 797 (1957]].The crosslinking of the acrylate-type polymers already prepared is also achieved in that the alcohol radical of the ester contains reactive groups, e.g. epoxy [A. Berlin: Vyso252738 komol. Sojed. 1, 962 (1959)]. These groups react at elevated temperature with each other or with other suitable multifunctional agents such as e.g. phenol-formaldehyde resols, thereby inducing cross-linking of the macromolecules of the acrylate polymer [P. F. Sanders: C. 7,797 (1957)].
Podstata sposobu sieťovania polymérov a kopolymérov nenasýtených organických kyselin, ich esterov a ich anhydridov podfa vynálezu spočívá v tom, že sa tieto polyméry alebo kopolyméry zohrievajú na teplotu 20 až 240 °C v přítomnosti 0,05 až 10 % hmot. sieťovadla, ktorým sú alkyléndiamíny obecného vzorca IThe principle of the cross-linking process of the polymers and copolymers of unsaturated organic acids, their esters and their anhydrides according to the invention is that these polymers or copolymers are heated to a temperature of 20 to 240 ° C in the presence of 0.05 to 10% by weight. crosslinkers which are alkylenediamines of the general formula I
HzN—(CH2)n—NH2 (I) kde n je 2 až 12, alebo polyalkylénpolyamíny obecného vzorca IIH 2 N - (CH 2) n - NH 2 (I) wherein n is 2 to 12, or polyalkylene polyamines of formula II
H3N— [ (CH3)mNH(CH2)„ ]NH, (Π) o molekulovej hmotnosti 100 až 5' 000 g.H 3 N - [(CH 3 ) m NH (CH 2 ) n] NH, (Π) having a molecular weight of 100 to 5,000 g.
. mól1, kde m a n je 2 až 12 a x je určené molekulovou hmotnosťou zlúčeniny II.. mole 1 , where man is 2 to 12 and x is determined by the molecular weight of compound II.
Sieťujúce činidlo sa dávkuje do polymerizačnej násady pri príprave polymérú, alebo na povrch termoplastu před lisováním, alebo do lisovacej formy, alebo do taveniny polyméru počas tvarovania výrobku.The crosslinking agent is metered into the polymerization batch during the preparation of the polymers, or onto the surface of the thermoplastic prior to compression, or into the mold, or into the polymer melt during molding of the article.
Výhodou navrhovaného postupu podfa tohto vynálezu je to, že sieťovanie prebieha pri teplotách spracovania komerčných typov akrylátových a metakrylátových termoplastov v technologicky využitefnom čase, pričom hustotu polymérnej siete možno měnit v širokom rozsahu. Rovnako výhodná je tiež možnost úpravy len povrchových vrstiev výrobku a možnost regulácie hrůbky zosietenej vrstvy výrobku. Tieto úpravy zvýhodňujú použitie predmetov vyrobených z uvedených termoplastov zlepšením odolnosti proti vonkajším vplyvom, ako sú zvýšené teploty, posobenie rozpúšťadiel a mechanické odieranie.An advantage of the proposed process according to the invention is that the crosslinking takes place at processing temperatures of commercial types of acrylate and methacrylate thermoplastics at a technologically useful time, while the density of the polymer network can be varied over a wide range. Equally advantageous is also the possibility of modifying only the surface layers of the article and the possibility of regulating the depth of the cross-linked layer of the article. These treatments favor the use of articles made of said thermoplastics by improving resistance to external influences such as elevated temperatures, solvent deposition and mechanical abrasion.
Příklad 1Example 1
Do polymerizačnej násady na přípravu doškového polymetylmetakrylátu, ktorá pozostáva z 95,45 % hmot. metylmetakrylátu, 4,5 % hmot. dibutylftalátu a 0,05 % hmot. 2,2‘-azobisizohutyronitrilu sa pridajú tieto množstvá 1,3-diamínopropánu na 100 ml násady, a to 0,05, alebo 0,5, alebo 1, alebo 5 percent hmot. Polymerizácla prebiehala najskór v baničke pri miešaní a zvyšovaní teploty až na 70 °C v priebehu 30 minút, pričom spolymerizuje 8 až 10 % hmot. monoméru. Aparatúra sa sústavne prefukuje dusíkom 2 1. h_1. Potom sa predpolymér naplní do polymerizačných foriem zo silikátového skla. Hrúbka došky takto připraveného organického skla je 3 mm. Reakcia prebieha v teplovzdušnej sušiarni po dobu 18 hodin pri teplote 40 °C a ukončí sa zohriatím dosiek vo vodnom kúpeli na teplotu 95 °C počas 1 hodiny. Zo získaných dosiek sa odoberú vzorky polymérú, ktoré sa temperujú pri teplote 180 °C v uzatvorených formách alebo ampulkách. Množstvo v chloroforme nerozpustného polymeru po sof-gél analýze pri teplote 20 °C je následovně: po 20 minútovej temperách 0, 77, 84, 89 % hmot.; po 40 minútovej temperách 18, 88, 89, 93 °/o hmot. ak příměs 1,3-diamínopropánu vo vzorke polymetylmetakrylátu je 0,05, alebo 0,5. alebo 1, alebo 5 % hmotnostných.Into the polymerization batch for the preparation of thatched polymethyl methacrylate, which consists of 95.45 wt. % methyl methacrylate, 4.5 wt. % dibutyl phthalate and 0.05 wt. 2,2'-azobisisohutyronitrile, these amounts of 1,3-diamino propane per 100 ml of feed are added at 0.05, or 0.5, or 1, or 5 percent by weight. The polymerization proceeded first in the flask while stirring and raising the temperature up to 70 ° C over 30 minutes, co-polymerizing 8 to 10 wt. monomer. The apparatus is continuously purged with nitrogen 2 L h -1 . The prepolymer is then filled into polymeric molds of silicate glass. The thickness of thatched organic glass is 3 mm. The reaction is carried out in a hot-air oven for 18 hours at 40 ° C and terminated by heating the plates in a water bath at 95 ° C for 1 hour. Polymer samples are taken from the obtained plates and are tempered at 180 ° C in closed molds or ampoules. The amount of chloroform-insoluble polymer after analysis at 20 ° C is as follows: after 20 minutes at 0, 77, 84, 89% by weight; after 40 min. temperatures of 18, 88, 89, 93% w / w. and wherein the addition of 1,3-diamino propane in the sample of polymethyl methacrylate is 0.05, or 0.5. or 1, or 5% by weight.
Příklad 2Example 2
Postupuje sa ako v příklade 1 s tým rozdielom, že ako siefujúca příměs sa použije 1.6-diamínohexán, pričom sa získajú analogické výsledky. Po temperovaní připraveného polymérú pri teplote 180 °C tvoří množstvo zosieteného polymérú po rozpúšfaní v chloroforme pri teplote 20 °C vo vzorkách polymetylmetakrylátu nasledujúci podiel: po temperách 10, 20, 40, 60, 90 minút 0, 41, 86, 93 a 100 % hmot. ak sa přidá 0,5 °/o hmot. diamínu a 0, 88, 97, 99 a 100 °/o hmot., ak sa přidá do systému 1 % hmot. diamínu. Příklad 3The procedure was as in Example 1 except that 1,6-diamino hexane was used as the crosslinking agent, and analogous results were obtained. After tempering the prepared polymer at 180 ° C, the amount of crosslinked polymer when dissolved in chloroform at 20 ° C in the samples of polymethyl methacrylate is as follows: after temperatures of 10, 20, 40, 60, 90 minutes 0, 41, 86, 93 and 100% wt. when 0.5% w / w is added. % of diamine and 0, 88, 97, 99 and 100 wt. diamine. Example 3
Postupuje sa ako v příklade 1 s tým rozdielom, že ako siefujúca příměs sa dá 1,12-diamínododekán. Po temperovaní připraveného polymérú pri teplote 180 °C sa polymér rozpúšťa v chloroforme pri teplote 20 CC. Nerozpustný polymér tvoří nasledujúcu časť zo vzorky: po temperách 10, 20, 60, 90 minút a pri koncentrácii diamínu 0,1 % hmot., 0, 0, 0, 52, a 60 % hmot., pri koncentrácii diamínu 0,5 % hmot., 0, 28, 56, 63 a 94 % Příklad 4The procedure is as in Example 1, except that 1,12-diamine dodecane is used as the crosslinker. After tempering the prepared polymer at 180 ° C, the polymer dissolves in chloroform at 20 ° C. The insoluble polymer forms the following sample portion: after temperatures of 10, 20, 60, 90 minutes and at a diamine concentration of 0.1% by weight. , 0, 0, 52, and 60% by weight, at a diamine concentration of 0.5% by weight, 0, 28, 56, 63 and 94%.
Perlový polymetylmetakrylát zrnenia 0,1 až 0,25 mm sa naimpregnoval roztokom 1,6-diamínohexánu v etanole. Po odpaření rozpúšfadla a difúzii reagentu do polymérnych častíc sa takto upravený vstrekovací materiál temperuje pri teplotách 100 až 240 °C v zatavených ampulkách, alebo v lisovacej formě. Rýchlosť sieťovania a čas potřebný na vznik nerozpustného polymérú vo vzorke sú pri koncentrácii diamínu 0,108 mól. kg1 v závislosti cd teploty reakcie následovně: pri teplote 100, 140, 180 a 240 °C je rýchlosť vzniku gélu 0,05, 0,58, 5,9 a 45 % hmot. . . min“1, a do vzniku gélu uplynie čas 2 000, 220, 19 a 3 minúty.The pearl polymethyl methacrylate of 0.1 to 0.25 mm grain size was impregnated with a solution of 1,6-diamino hexane in ethanol. After evaporation of the solvent and diffusion of the reagent into the polymer particles, the injection material so treated is tempered at temperatures of 100 to 240 ° C in sealed ampoules or in a mold. The crosslinking rate and time required to form insoluble polymers in the sample at a diamine concentration of 0.108 mol. kg 1 depending on the reaction temperature cd as follows: at 100, 140, 180 and 240 ° C the gel formation rate is 0.05, 0.58, 5.9 and 45 wt. . . min -1 , and a time of 2,000, 220, 19 and 3 minutes elapses before the gel is formed.
P r í k 1 a d 5Example 5
Pcstupuje se ako v příklade 4 s tým rozdielom, žs ako sietujúce činidlo sa přidá k perlovému polymeíylmetakrylátu 1,2-diamínoetán. Potom pri 140 °C nerozpustný podiel vo vzorke možno zistiť po 360 minutách a rychlost vytvárania gélu je 2,3 % hmot. za minutu. Ak sa pracuje pri teplote 180 °C indukčný čas sa skráti na 28 minút a rýchlosť vytvárania genu je 2,3 % hmot. . min-1.The procedure is as in Example 4, except that 1,2-diaminoethane is added as the crosslinking agent to the bead polymethyl methacrylate. Then, at 140 ° C, the insoluble portion of the sample can be detected after 360 minutes and the gel formation rate is 2.3% by weight. per minute. When working at 180 ° C, the induction time is reduced to 28 minutes and the rate of gene formation is 2.3% by weight. . min -1 .
P r í k 1 a d 6Example 6
Vzorky připravené ako v příklade 4 s tým rozdielom, že ako sietujúce činidlo sa použije 1,12-diamínododekán nanesený na perličky polymeíylmetakrylátu. Pri teplote 180 stupňov Celsia sa polymér zosieťuje rýchlosťou 9,1 % hmot. . min“1 a doba do vzniku gélu je 15 min.Samples prepared as in Example 4, except that 1,12-diamine dodecane applied to the polymethyl methacrylate beads was used as the crosslinking agent. At 180 degrees Celsius, the polymer crosslinked at a rate of 9.1 wt. . min -1 and the time to gel formation is 15 min.
Příklad 7Example 7
Kopolymér vhodný pre· sieťovanie diamínmi pri teplote 20 °C sa připravuje tak, že do 900 ml sušeného xylenu sa dávkuje 150 ml etylakrylátu, 130 ml butylakrylátu, 270 ml metylmetakrylátu a 80 g maleinanhydridu. Přidá sa ešte regulátor molekulovej hmotnosti n-dodecyltio-1 v množstve 0,45 ml. Ako iniciátor polymerizácie sa použije terc.butylperbenzoát 3 ml. Polymerizácia prebieha pri teplote 110 C, v dusíkovej atmosféře, 6 hodin. Z připraveného roztoku kopolyméru sa nanesú na sklenenú podložku vrstvy o hrúbke 20 (Um. Po odpaření rozpúšťadla sa filmy kopolyméru vystavia účinkom pár diaminu obecného vzorca I.A copolymer suitable for diamine crosslinking at 20 ° C is prepared by adding 150 ml of ethyl acrylate, 130 ml of butyl acrylate, 270 ml of methyl methacrylate and 80 g of maleic anhydride to 900 ml of dried xylene. A molecular weight regulator of n-dodecylthio-1 in an amount of 0.45 ml was added. 3 ml of tert-butyl perbenzoate is used as polymerization initiator. The polymerization is carried out at 110 DEG C., under nitrogen, for 6 hours. From the prepared copolymer solution, 20 [mu] m thick layers are applied to the glass substrate.
HzN—(CH2)n—NH2 (I) kde n je 2 až 12, pri teplote 20 °C.H 2 N - (CH 2) n - NH 2 (I) wherein n is 2 to 12, at 20 ° C.
Rýchlosť sietovania je 0,95 % hmot. polymérneho gélu za hodinu ako vo vzorci I je n 6.The crosslinking rate is 0.95 wt. of the polymer gel per hour as in Formula I is n6.
Příklad 8Example 8
Perlový polymetylmetakrylát použitý ako v příklade 4 sa naimpregnuje polyalkyénpolyamínom obecného vzorca IIThe pearl polymethyl methacrylate used as in Example 4 is impregnated with a polyalkylene polyamine of the formula II
H,tN— [ (CH·, jmNH (CH,), ] ΝΗτ (H) pričom man može mať hodnotu 2 až 12 ia x je určené priemernou molekulovou hmot-.H, t N - [(CH ·, j m NH (CH 2),] ΝΗτ (H) where m and n can be between 2 and 12 µ and x is determined by the average molecular weight.
nosťou polyalkylénpolyamínu. Po zahriatí naimpregnovaného polyméru, ktorý obsahuje 1 % hmot. zlúčeniny II s priemernou M. h. 100, a m a n vo vzorci II je 2, na teplotu 140 °C, vytvoří sa za 4 hodiny 87 % hmot. gélu. Pri temperovaní na teplotu 220 °C, 87 % hmot. gélu vznikne už po 15 minútach. Polymér s naneseným polyalkylénpolyamínom v množstve 1 % hmot., pričom m a n vo vzorci II je 6 a riemerná M. h. je 1 000, temperuje sa pri teplote 220 °C 15 až 30 minút, poskytne produkt s obsahom gélu 92 a 97 % hmot. Primiešanie 10 % hmot. polyalkylénpolyamínu s priemernou M. h. 5 000, pričom m a n vo vzorci II je 12 k perlovému polyrnetylmetakrylátu umožňuje zosietit po temperovaní polyméru pri teplote 140%: za 1/2, 1 a 4 hodiny 64, 84, a 100 % hmot. vzorky. Molekulové hmotnosti sú uvedené v g . mól na _1.by polyalkylene polyamine. After heating the impregnated polymer containing 1 wt. Compound II with an average M. h. 100, the amine in formula II is 2, at a temperature of 140 ° C, 87% wt. gel. When tempered to 220 ° C, 87 wt. gel is formed after 15 minutes. Polymer loaded with polyalkylene polyamine in an amount of 1% by weight, wherein the man in formula II is 6 and the average M. h. is 1000, tempered at 220 ° C for 15 to 30 minutes to give a product with a gel content of 92 and 97 wt. 10% wt. polyalkylene polyamine with an average M. h. 5,000, wherein the man in formula II is 12 to pearl poly (methyl methacrylate) makes it possible to crosslink after tempering the polymer at 140%: at 1/2, 1 and 4 hours 64, 84, and 100 wt. samples. Molecular weights are given in g. mole to _1 .
Příklad. 9Example. 9
V laboratórnotn vstrekovacom zariadení pre přípravu diskov alebo doštičiek z termoplaste v s hrubkou výlisku 2 mm a hmotnosfou do 5 g, sa v tavnéj komoře nahřeje polymetakrylátový granulát s M. li. 8.104 gramov . mól1 na teplotu 240 °C, vstrekovacia forma sa temperuje na teplotu 140 °C a před jej uzatvorením sa do· nej dá 0,15 g 1,6-diamínohexánu. Hned' nato sa uskutoční vstreknutie taveniny polymetylmetakrylátu. Po 5 minútach sa zahájí chladenie a pri 70 stupňov Celsia sa vyberie disk polymetylmetakrylátu, ktorý podfa rozpustnosti v chloroforme obsahuje 43 % hmot. gélu. Podobný výsledok sa dosiahne aj s 1,12-diamínododekánom a s polyalkylénpoiyamími s M. h. 100 až 5 000 g . mól“1. Ak sa do formy nepřidá viacfunkčný amin, výlisok je v chloroforme celkom rozpustný.Polymethacrylate granulate with M.I. is heated in a melting chamber in a laboratory injection molding machine for the preparation of thermoplastic discs or plates with a thickness of 2 mm and a weight of up to 5 g. 8.10 4 grams. mole 1 to 240 [deg.] C., the injection mold is heated to 140 [deg.] C. and 0.15 g of 1,6-diamino-hexane is introduced into the injection mold before it is closed. Immediately thereafter, the melt injection of the polymethyl methacrylate is carried out. After 5 minutes, cooling was started and a polymethyl methacrylate disc containing 43% by weight solubility in chloroform was removed at 70 degrees Celsius. gel. A similar result is obtained with 1,12-diamino-dodecane and polyalkylene polyamines with M. h. 100 to 5,000 g. mole “ 1 . If the multifunctional amine is not added to the mold, the molding is completely soluble in chloroform.
Příklad 10Example 10
Použije sa vstrekovacie zariadenie ako v příklade 9 s tým rozdielom, že vstrekovacia hlava má přídavné zariadenie. ktoré dávkuje sieťujúcu příměs do taveniny polyméru v mieste hubice. Podiel zosieteného polymeru vo výlisku je 80 °/o hmot. pri dávke 0,15 gramov 1,6-diamínohexánu na 5 g taveniny polyméru.An injection device is used as in Example 9 except that the injection head has an additional device. which dispenses the crosslinking agent into the melt of the polymer at the nozzle site. The proportion of crosslinked polymer in the molding is 80% by weight. at a dosage of 0.15 grams of 1,6-diamino-hexane per 5 grams of polymer melt.
Příklad 11Example 11
Na etanolom umytu polymetylmetakrylátovú došku o hrúbke 5 mm sa nanesie etanolový roztok 1,6-diamínohexánu. Po odpaření etanolu sa došky uzatvoria medzi silikátové sklá a temperujú sa rózny čas pri teplote 180 °C. Po temperovaní 5, 10, 20, 40, minút pri obojstrannom nánose siefovadla 0,5 % hmot. nerozpustný podiel došky tvoří 0, 63, 81, 80 % hmot. a pri nánose 0,9 % hmot. siefovadla nerozpustný podiel došky je 3, 92, 99 % hmot.An ethanolic solution of 1,6-diamino hexane is applied to a 5 mm thick polymethylmethacrylate thatch in ethanol. After evaporation of the ethanol, the thatch is sealed between silicate glasses and tempered for a different time at 180 ° C. After tempering for 5, 10, 20, 40 minutes with a crosslinker coating of 0.5% by weight. the insoluble fraction of thatch is 0, 63, 81, 80 wt. and at a loading of 0.9 wt. the insoluble thatched portion is 3.92, 99% by weight.
Příklad 12Example 12
Kopolymér styrénu s 5 % hmot., alebo 15 % hmot. kyseliny undecénovej, alebo s 5 % hmot., alebo 15 % hmot. kyseliny itakonovej sa granuluje a potom sa impregnuje 1,12-diamínododekánom tak, aby po vysušení granulát obsahoval 1,2 % hmot. diaminu. Po následnej temperách v zatavených ampulkách pri teplote 155 °C počas 60 minút je 38 a 40 % hmot. vzorky nerozpustných v chloroforme.Styrene copolymer with 5 wt.% Or 15 wt. undecenoic acid, or with 5 wt.% or 15 wt. itaconic acid is granulated and then impregnated with 1,12-diamino-dodecane so that after drying the granulate contains 1.2 wt. diamine. After subsequent temperatures in sealed ampoules at 155 ° C for 60 minutes, 38 and 40 wt. samples insoluble in chloroform.
Přiklad .13Example .13
Rovnakým spůsobom ako v příklade 12 sa připraví kopolymér styrénu s tým rozdielom, že sa použije ako komonomér metylmetakrylát, alebo butylakrylát v množstve 5 alebo 15 % hmot. Granulát z vyššie uvedených kopolymérov sa impregnuje etanolovým roztokom polyalkylénpolyamínu o M. h. 1000 gramov. mól-1, rovnakého vzorca ako zlúčeniny II v příklade 8, tak, aby po odpaření rozpúšťadla na povrchu granulí zostalo 5 % hmot. sieťovadla. Takto upravený polymér sa temperuje v zatavených ampulkách pri teplote 155 °C a po 60 minútach je 651 °/o hmot. kopolyméru nerozpustných v chloroforme.The styrene copolymer was prepared in the same manner as in Example 12 except that methyl methacrylate or butyl acrylate was used as comonomer in an amount of 5 or 15% by weight. The granulate of the above copolymers is impregnated with an ethanolic solution of polyalkylene polyamine of M.h. 1000 grams. mole -1 , of the same formula as compound II in Example 8, so that 5% by weight of the granules remain on the granule surface after evaporation of the solvent. crosslinking. The polymer thus treated is tempered in sealed vials at 155 ° C and after 60 minutes is 651% w / w. chloroform-insoluble copolymer.
Spůsob sieťovania polymérov alebo kopolymérov nenasýtených organických kyselin, ich esterov a ich anhydridov viacfunkčnými amínmi může nájsť široké uplatnenie v chémii polymérov, predovšetkým pri modifikácii polyakrylátov a polymetakrylátov a v priemysle výroby a spracovania plastických látok.The process of crosslinking polymers or copolymers of unsaturated organic acids, their esters and their anhydrides with multifunctional amines can find wide application in the polymer chemistry, especially in the modification of polyacrylates and polymethacrylates and in the plastics manufacturing and processing industry.
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