SK8452000A3 - Method for producing cellular plastics - Google Patents
Method for producing cellular plastics Download PDFInfo
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- SK8452000A3 SK8452000A3 SK845-2000A SK8452000A SK8452000A3 SK 8452000 A3 SK8452000 A3 SK 8452000A3 SK 8452000 A SK8452000 A SK 8452000A SK 8452000 A3 SK8452000 A3 SK 8452000A3
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- water
- carbon atoms
- blowing
- blowing agents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 230000001413 cellular effect Effects 0.000 title claims description 4
- 239000004033 plastic Substances 0.000 title abstract description 5
- 229920003023 plastic Polymers 0.000 title abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000007858 starting material Substances 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- -1 alkyl radicals Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002991 molded plastic Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 238000005187 foaming Methods 0.000 claims description 2
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- KQBTUOVABZLXGP-UHFFFAOYSA-N butane-1,4-diol;ethane-1,2-diol Chemical compound OCCO.OCCCCO KQBTUOVABZLXGP-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006250 specific catalysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2410/00—Soles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
SPÔSOB VÝROBY CELULÁRNYCH PLASTOVMETHOD OF PRODUCTION OF CELLULAR PLASTICS
Oblasť technikyTechnical field
Vynález sa týka výroby tvarovaných plastov na báze polyuretánu z polyéterpolyolov a izokyanátových predpolymérov s použitím vody ako nadúvadla a s použitím špecifickej katalýzy so zlepšeným výťažkom plynu a zlepšenými reakčnými vlastnosťami.The invention relates to the production of molded polyurethane-based plastics from polyether polyols and isocyanate prepolymers using water as a blowing agent and using specific catalysis with improved gas yield and improved reaction properties.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Výroba prípadne celulárnych tvarovaných plastov na báze polyuretánu (PUR) so zhutneným povrchom patrí už dlho ku stavu techniky, ako je US-A 40 65 410, US-A 42 18 543, 37 26 952, 13 65 215, 40 33 912, 40 24 090, 40 58 492, 40 98 731,44 77 602, EP-A 17 928, 44 481 a DE-A 31 33 859.The production of optionally compacted polyurethane (PUR) molded plastics having a compacted surface has long been known in the art, such as US-A 40 65 410, US-A 42 18 543, 37 26 952, 13 65 215, 40 33 912, 40 24 090, 40 58 492, 40 98 731.44 77 602, EP-A 17 928, 44 481 and DE-A 31 33 859.
Tieto tvarované plasty boli tiež používané rad rokov na výrobu podrážok obuvi. Obísť sa bez použitia určitých, halogén obsahujúcich nadúvadiel, ako je monofluórtrichlórmetán (R 11) alebo sekundárnych produktov R 141b a R 134a a nadúvania vodou vedie k technickým problémom, ktoré neboli doposiaľ úplne vyriešené.These molded plastics have also been used for many years to produce shoe soles. Bypassing certain halogen-containing blowing agents, such as monofluorotrichloromethane (R 11) or secondary products R 141b and R 134a, and water swelling leads to technical problems that have not yet been fully solved.
Ak je použitá voda, vznikajú hlavne nasledujúce problémy a obtiaže: čas zdržania pri tvarovaní s pozadím rozmerovej stability v dôsledku tendencie sa rozopínať alebo narastať, pretože tvarové diely pri predchádzajúcich, obvykle používaných časoch, ešte nemôžu byť vystavené zaťaženiu; toto môže byť kompenzované dlhšími časmi zdržania pri tvarovaní, ale výsledkom je pokles produktivity.In particular, when water is used, the following problems and difficulties arise: dwell time in forming with a dimensional stability background due to the tendency to expand or build up, since the molded parts cannot be subjected to the load at previous, commonly used times; this can be compensated by longer molding residence times, but the result is a decrease in productivity.
Ďalšou veličinou je užší pomer zhutnenia, to znamená kvocient surovej hmotnosti tvarového dielu a surovej hmotnosti voľnej peny. Zatiaľ čo boli skôr používané stupne zhutnenia až do 2,8, pomer pre vodu je podľa skúseností medzi 1,7 a 2,1. Pri vyšších hodnotách je výsledkom rozpínanie a pri nižších hodnotách sú výsledkom problémy s plnením formy.Another variable is the narrower compaction ratio, i.e. the quotient of the molded part weight and the free foam part weight. While compaction grades of up to 2.8 have previously been used, the water ratio is experienced between 1.7 and 2.1. At higher values, expansion results and at lower values results in mold filling problems.
31469/H31469 / H
Podstata vynálezuSUMMARY OF THE INVENTION
Teraz bolo zistené, že použitím určitých kovových katalyzátorov môže byť dosiahnutý vysoký výťažok plynu s vodou ako nadúvadlom a zostávajú zachované skôr dosahované dobré mechanické vlastnosti.It has now been found that by using certain metal catalysts, a high gas yield with water as a blowing agent can be achieved and good mechanical properties previously achieved are retained.
Predmetom predloženého vynálezu je spôsob výroby celulámych tvarovaných plastov na báze poiyéter-polyuretánu vypenením vo forme reakčnej zmesi zIt is an object of the present invention to provide a process for the production of cellulosic polyurethane molded plastics by foaming in the form of a reaction mixture of
A) najmenej jednej polyéter- a/alebo polyester-polyolovej zložky s vyššou molekulárnou hmotnosťou,(A) at least one higher molecular weight polyether and / or polyester polyol component,
B) izokyanátovej zložky,B) isocyanate component,
C) predlžovačov reťazcov,(C) chain extenders;
D) nadúvadiel,D) blowing agents,
E) aminových a kovových aktivátorov a(E) amine and metal activators; and
F) ďalších známych pomocných látok a prísad udržovaním charakteristického indexu 70 až 130, ktorého podstata spočíva v tom, že sa ako nadúvacia zložka D) použije voda, pripadne s pridaním organických nadúvadiel a zložka aktivátora E) obsahuje zlúčeninu cínu všeobecného vzorca (i)F) other known excipients and additives by maintaining a characteristic index of 70 to 130, characterized in that water is used as the blowing component D), optionally with the addition of organic blowing agents, and the activator component E) contains a tin compound of the formula (i)
(I).(I).
v ktoromin which
R1, R2 znamenajú identické alebo rôzne alkylové zvyšky s 1 až 10 uhlíkovými atómami alebo arylové zvyšky so 6 až 10 uhlíkovými atómami alebo arylalkylové zvyšky a n znamená číslo od 1 do 4, výhodne 1, 2, 3 alebo 4.R 1 , R 2 are identical or different alkyl radicals of 1 to 10 carbon atoms or aryl radicals of 6 to 10 carbon atoms or arylalkyl radicals and n is a number from 1 to 4, preferably 1, 2, 3 or 4.
31469/H31469 / H
Zložka polyéter-polyolu A) s vyššou molekulárnou hmotnosťou má priemernú OH-funkcionalitu 1,95 až 2,95 a je výhodne zmesouThe higher molecular weight polyether-polyol component A) has an average OH functionality of 1.95 to 2.95 and is preferably a mixture of
Aa) najmenej jedného polyéter-polyolu s OH-číslom v rozsahu 21 až 112, ktorý je získaný alkoxyláciou bifunkčného štartéra, napríklad propylénoxidom ako i etylénoxidom s prevažne primárnymi OH skupinami aAa) at least one polyether polyol having an OH number in the range of 21 to 112 which is obtained by alkoxylation of a bifunctional starter, for example propylene oxide as well as ethylene oxide having predominantly primary OH groups, and
Ab) najmenej jedného polyéter-polyolu s OH-číslom v rozsahu 20 až 56 a s funkcionalitou štartéra 2,5 až 3,5, ktorý je získaný alkoxyláciou zodpovedajúceho štartéra alebo zmesou štartérov, napríklad propylénoxidom a etylénoxidom s prevažne primárnymi OH koncovými skupinami.Ab) at least one polyether polyol having an OH number in the range of 20 to 56 and a starter functionality of 2.5 to 3.5 which is obtained by alkoxylation of the corresponding starter or a mixture of starters, for example propylene oxide and ethylene oxide with predominantly primary OH end groups.
Tieto polyoly môžu obsahovať obvyklé plnidlá, ktoré sú získané očkovaním pomocou styrénu/akrylonitrilu alebo vo forme disperzií polymočoviny adíciou diamínov a diizokyanátov do polyolov.These polyols may contain conventional fillers which are obtained by grafting with styrene / acrylonitrile or in the form of polyurea dispersions by addition of diamines and diisocyanates to the polyols.
Zložka polyizokyanátu B) je predpolymér s obsahom NCO 10 až 25 % hmotnostných. Zložka je pripravená reakciou i) diizokyanátodifenylmetánu s ii) zložkou polyolu s rozsahom OH-čísla 20 až 112 a s priemernou OH funkcionalitou 2,0 až 2,5 pričom zložka i) môže obsahovať karbodiimidové skupiny.The polyisocyanate component B) is a prepolymer with an NCO content of 10 to 25% by weight. The component is prepared by reacting i) a diisocyanatodiphenylmethane with ii) a polyol component having an OH-range of 20 to 112 and an average OH functionality of 2.0 to 2.5, wherein component i) may contain carbodiimide groups.
Glykoly, ako je 1,2-etándiol a 1,4-butándiol a podobne, sú používané ako zložka C).Glycols such as 1,2-ethanediol and 1,4-butanediol and the like are used as component C).
Ako aktivátory D) na amínovej strane prichádzajú do úvahy trietyléndiamín, N-metylimidazol a Ν,Ν-dimetylbenzylamín, ktoré môžu byť tiež čiastočne neutralizované, ako i prípadne známe cínaté alebo cíničité karboxyláty alebo merkaptidy.Suitable activators D) on the amino side are triethylenediamine, N-methylimidazole and Ν, Ν-dimethylbenzylamine, which can also be partially neutralized, as well as possibly known stannous or tin carboxylates or mercaptides.
Ako ďalšie pomocné látky a prísady F), ktoré môžu byť prípadne používané, je možné uviesť povrchovo aktívne látky, penové stabilizátory, celulárne regulátory, oddeľovacie činidlá, farbivá, pigmenty, hydrolyzačné stabilizátory, protiplesňové a protíbakteríálne látky, svetelné a oxidačné stabilizátory alebo antistatické prostriedky.Other adjuvants and additives F) which may optionally be used include surfactants, foam stabilizers, cellular regulators, detaching agents, dyes, pigments, hydrolyzing stabilizers, antifungal and antibacterial agents, light and oxidizing stabilizers or antistatic agents. .
Na vykonanie spôsobu podľa vynálezu sú východiskové materiály používané v množstvách, ktoré zodpovedajú izokyanátovémuTo carry out the process according to the invention, the starting materials are used in amounts corresponding to isocyanate
31469/H charakteristickému indexu 70 až 130, hlavne 90 až 110. „Izokyanátový charakteristický index,, je tu chápaný ako kvocient počtu izokyanátových skupín a počtu skupín, ktoré sú reaktívne voči izokyanátovým skupinám, vynásobenýThe "isocyanate characteristic index" is understood here as the quotient of the number of isocyanate groups and the number of groups that are reactive to isocyanate groups, multiplied by
100.100th
Postup vykonania spôsobu podľa vynálezu je analogický so skôr známymi postupmi. Všeobecne to znamená, že zložky A) a C) až F) sa spoja na „polyolovú zložku,, a reagujú s polyizokyanátovou zložkou B) v jednom stupni v uzatvorenej forme, napríklad uzatvorenej forme z kovu alebo plastu, pričom sú používané obvyklé dvojzložkové miesiace jednotky. Množstvo reakčnej zmesi, zavedené do formy a tiež množstvo vody, použité ako nadúvadlo je vybrané v rozsahu vyššie uvedených rozmedzí tak, aby tvarované penové hmoty mali surovú hustotu 150 až 1000 kg/m3. Produkty spôsobu podľa vynálezu sú polotuhé penové hmoty so zhutneným povrchom, to znamená ich Shore A tvrdosť podľa DIN 53 505 je v rozsahu od 15 do 75.The process according to the invention is analogous to the known processes. Generally, components A) and C) to F) are combined to form a "polyol component" and react with the polyisocyanate component B) in one step in a closed form, for example a closed form of metal or plastic, using conventional two-component kneading agents. unit. The amount of reaction mixture introduced into the mold as well as the amount of water used as blowing agent is selected within the above ranges so that the molded foams have a crude density of 150 to 1000 kg / m 3 . The products of the process according to the invention are semi-rigid foams having a compacted surface, i.e. their Shore A hardness according to DIN 53 505 ranges from 15 to 75.
Ich najdôležitejší odbor použitia je výroba obuvi, napríklad na penové podrážky obuvi alebo vsádzané časti obuvi.Their most important field of application is the manufacture of footwear, for example for foam soles of shoes or shoe inserts.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
V nasledujúcich príkladoch bol udržovaný izokyanátový charakteristický index 100. Mechanické vlastnosti boli stanovené na testovacích vzorkách s rozmermi 20 x 20 x 1 cm. Všetky percentuálne údaje sa vzťahujú na hmotnostné percentá.In the following examples, an isocyanate characteristic index of 100 was maintained. Mechanical properties were determined on test specimens of 20 x 20 x 1 cm. All percentages are by weight.
Východiskové materiályStarting materials
A) PolyéterpolyolA) Polyether polyol
A1) Polyéterpolyol s OH-číslom 28 so 70 % propylénoxidu a 30 % etylénoxidu a prevažne primárnymi OH skupinami a s propylénglykolom ako štartérom,A1) Polyether polyol with OH number 28 with 70% propylene oxide and 30% ethylene oxide and predominantly primary OH groups and with propylene glycol as a starter,
31469/H31469 / H
Α2) Polyéterpolyol s OH-číslom 25 s 80 % propylénoxidu a 20 % etylénoxidu a prevažne primárnymi OH skupinami a s trimetylolpropánom ako štartérom,Α2) Polyether polyol with OH number 25 with 80% propylene oxide and 20% ethylene oxide and predominantly primary OH groups and with trimethylolpropane as starter,
A3) Polyéterpolyol s OH-číslom 56 z propylénoxidu s propylénglykolom ako štartérom,A3) Polyether polyol with OH number 56 of propylene oxide with propylene glycol as starter,
A4) Polyéterpolyol s OH-číslom 56 z propylénoxidu s trimetylolpropánom ako štartérom,A4) Polyether polyol with OH number 56 from propylene oxide with trimethylol propane as starter,
B) PolyizokyanátB) Polyisocyanate
B1) Predpolymér, pripravený reakciou 56 hmotnostných dielov 4,4‘diizokyanátdifenylmetánu (MDI) a 2 hmotnostných dielov modifikovaného MDI s obsahom NCO 30 %, pripraveného čiastočnou karbodiimidáciou a zmesou polyolov z 37 hmotnostných dielov polyolu A3) a 5 hmotnostných dielov polyolu A4), pričom sa dosiahne obsah NCO 17,5 %,B1) A prepolymer prepared by reacting 56 parts by weight of 4,4'-diisocyanate diphenylmethane (MDI) and 2 parts by weight of modified MDI containing 30% NCO, prepared by partial carbodiimidation and a mixture of polyols of 37 parts by weight of polyol A3) and 5 parts by weight of polyol A4). achieving an NCO content of 17,5%,
C) Katalyzátor podľa vynálezuC) Catalyst according to the invention
Dibutylcínsulfid.Dibutylcínsulfid.
12,45 g oxidu dibutylcínoxidu sa pridá do roztoku 24 g Na2S . 9 H2O a 200 ml vody a 5 ml etanolu a potom sa po kvapkách pridá 12 g kyseliny octovej. Zmes sa mieša pri teplote miestnosti počas 1 hodiny, potom sa pridá 100 ml metylénchloridu, zmes sa pretrepe a rozdelí sa. Po zahustení sa získa12.45 g of dibutyltin oxide are added to a solution of 24 g of Na 2 S. 9 H 2 O and 200 ml of water and 5 ml of ethanol, and then 12 g of acetic acid are added dropwise. The mixture is stirred at room temperature for 1 hour, then 100 ml of methylene chloride are added, the mixture is shaken and partitioned. After concentration, it is obtained
9,8 g dibutylcínsulfidu.9.8 g of dibutyltin sulphide.
Analýza: S stanovená: 12,5; vypočítaná: 12,3 %, molekulárna hmotnosť 795 g/mol (osmometricky);Analysis: S determined: 12.5; calculated: 12.3%, molecular weight 795 g / mol (osmometrically);
n = 3; monomérna molekulárna hmotnosť 264 g.n = 3; monomer molecular weight 264 g.
31469/H <o31469 / H <o
Tabuľka 1Table 1
31469/H31469 / H
31469/Η31469 / Η
Dibutylcínsulfid, ako katalyzátor podľa vynálezu, dáva výnimočne vysoký výťažok plynu, pričom štartovací čas zostáva prakticky nezmenený dokonca i pri vyšších koncentráciách. Výhodný priebeh nadúvacej reakcie dokonca tiež umožňuje zníženie množstva vody bez významného zvýšenia surovej hustoty voľnej peny v porovnaní s katalýzou bez dibutylcínsulfidu. Výsledkom je možnosť nastavenia pomeru zhutnenia okolo 2,0, ktorý je ideálny pre systémy vodou nadúvaných podrážok. Problémy, ako je rozmerová stabilita alebo plniace vlastnosti formy, môžu byť v dôsledku toho tiež ovládané. Stavba polyméru končí skoro s nezmeneným štartovacím časom, takže je možné dosiahnuť celkovo kratšie časy uvoľnenia z formy bez zníženia kritického štartovacieho času pre formuláciu. Toto je vždy pozorované pri použití bežných aktivátorov. Tak príklady 2, 6 a 7 ukazujú konštantný štartovací čas, teda latentné správanie aktivácie podľa vynálezu napriek zvýšeniu množstva dibutylcínsulfidu.Dibutyltin sulphide, as the catalyst according to the invention, gives an exceptionally high gas yield, while the start time remains virtually unchanged even at higher concentrations. The preferred course of the blowing reaction even allows a reduction in the amount of water without significantly increasing the raw density of the free foam compared to catalysis without dibutyltin sulphide. As a result, it is possible to set a compaction ratio of about 2.0, which is ideal for water-puffed sole systems. As a result, problems such as dimensional stability or mold filling properties can also be controlled. The construction of the polymer ends with almost unchanged start time so that overall shorter release times can be achieved without reducing the critical start time for the formulation. This is always observed using conventional activators. Thus, Examples 2, 6 and 7 show a constant start time, i.e., the latent behavior of activation according to the invention despite an increase in the amount of dibutyltin sulphide.
Vhodnosť katalýzy podľa vynálezu je ďalej ukázaná tabuľkami 2 a 3 nižšie.The suitability of the catalysis according to the invention is further shown in Tables 2 and 3 below.
Cieľom spoľahlivej výroby, napríklad podrážok obuvi, by mal byť rozsah tolerancie pre zmršťovanie (skrátenie) podrážky v najlepšom prípade 0, maximálne 0,5 %, pretože nástroje sú nastavené na túto hodnotu. Ak je použité ako nadúvadlo voda, nastáva od určitého množstva vody (asi 0,35 dielu) opačný efekt, totiž nárast (roztiahnutie) tvarovanej hmoty. Tento prieťah má často za následok nepoužiteľnosť podrážky, pretože nárast je rôzny v pozdĺžnom a priečnom smere.The objective of reliable production, for example of shoe soles, should be the tolerance range for shrinking (shortening) the soles at best 0, maximum 0.5%, as the tools are set to this value. When water is used as a blowing agent, there is an opposite effect from a certain amount of water (about 0.35 parts), namely an increase in the molding mass. This delay often results in the inapplicability of the sole, as the growth varies in the longitudinal and transverse directions.
Tabuľka 2 - Požadovaný rozsah tolerancie scvrkávania 0 až maximálne 0,5 %Table 2 - Required range of shrinkage tolerance 0 to maximum 0,5%
31469/H31469 / H
Tabuľka 3 - Zväčšenie tvarovaného dielu o 0,5 % po čase zdržania vo forme 6 minútTable 3 - Enlargement of the molded part by 0.5% after a residence time of 6 minutes
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nie ánono Yes
Príklady 6 a 7 ukazujú obzvlášť výnimočne dobrý celkový výťažok a okrem toho môže byť hmota uvoľnená z formy po 3 minútach s rozmerovou stabilitou, pričom zmrštenie už zodpovedá ideálnemu stavu.Examples 6 and 7 show a particularly exceptionally good overall yield and, moreover, the mass can be released from the mold after 3 minutes with dimensional stability, the shrinkage already corresponding to the ideal state.
Bežná katalýza, ako v príklade 9, stále ešte vykazuje nárast (roztiahnutie) tvarového dielu po čase zotrvania vo forme 6 minút.Conventional catalysis, as in Example 9, still shows an increase (expansion) of the molded part after a residence time of 6 minutes.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19753723A DE19753723A1 (en) | 1997-12-04 | 1997-12-04 | Process for the production of cellular plastics |
| PCT/EP1998/007498 WO1999029751A1 (en) | 1997-12-04 | 1998-11-21 | Method for producing cellular plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SK8452000A3 true SK8452000A3 (en) | 2000-11-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SK845-2000A SK8452000A3 (en) | 1997-12-04 | 1998-11-21 | Method for producing cellular plastics |
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| Country | Link |
|---|---|
| EP (1) | EP1036104B1 (en) |
| AR (1) | AR016974A1 (en) |
| AU (1) | AU1488399A (en) |
| CZ (1) | CZ292074B6 (en) |
| DE (2) | DE19753723A1 (en) |
| DK (1) | DK1036104T3 (en) |
| ES (1) | ES2185235T3 (en) |
| HR (1) | HRP20000369A2 (en) |
| HU (1) | HUP0100492A2 (en) |
| ID (1) | ID25492A (en) |
| PL (1) | PL190884B1 (en) |
| PT (1) | PT1036104E (en) |
| SK (1) | SK8452000A3 (en) |
| WO (1) | WO1999029751A1 (en) |
| YU (1) | YU34000A (en) |
| ZA (1) | ZA9811054B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| MX2011007694A (en) * | 2011-07-19 | 2013-02-07 | Maria Eugenia Mena Navarro | Dielectric protective sole with high shape memory. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4043949A (en) * | 1975-03-06 | 1977-08-23 | M&T Chemicals Inc. | Oxidative stability of flexible polyurethane foams |
| US4136046A (en) * | 1976-05-20 | 1979-01-23 | M&T Chemicals Inc. | Storage-stable precursors for rigid polyurethane foams |
| US5646195A (en) * | 1995-03-07 | 1997-07-08 | The Dow Chemical Company | Catalyst for polyurethane carpet backings and carpets prepared therewith |
-
1997
- 1997-12-04 DE DE19753723A patent/DE19753723A1/en not_active Withdrawn
-
1998
- 1998-11-21 EP EP98958912A patent/EP1036104B1/en not_active Expired - Lifetime
- 1998-11-21 AU AU14883/99A patent/AU1488399A/en not_active Abandoned
- 1998-11-21 PT PT98958912T patent/PT1036104E/en unknown
- 1998-11-21 ID IDW20001053A patent/ID25492A/en unknown
- 1998-11-21 YU YU34000A patent/YU34000A/en unknown
- 1998-11-21 PL PL340692A patent/PL190884B1/en not_active IP Right Cessation
- 1998-11-21 ES ES98958912T patent/ES2185235T3/en not_active Expired - Lifetime
- 1998-11-21 CZ CZ20002045A patent/CZ292074B6/en not_active IP Right Cessation
- 1998-11-21 WO PCT/EP1998/007498 patent/WO1999029751A1/en not_active Ceased
- 1998-11-21 DE DE59806076T patent/DE59806076D1/en not_active Expired - Lifetime
- 1998-11-21 SK SK845-2000A patent/SK8452000A3/en unknown
- 1998-11-21 HR HR20000369A patent/HRP20000369A2/en not_active Application Discontinuation
- 1998-11-21 DK DK98958912T patent/DK1036104T3/en active
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- 1998-12-03 AR ARP980106140A patent/AR016974A1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2185235T3 (en) | 2003-04-16 |
| PL190884B1 (en) | 2006-02-28 |
| HUP0100492A2 (en) | 2001-12-28 |
| AU1488399A (en) | 1999-06-28 |
| EP1036104B1 (en) | 2002-10-23 |
| DE59806076D1 (en) | 2002-11-28 |
| DK1036104T3 (en) | 2003-02-17 |
| CZ292074B6 (en) | 2003-07-16 |
| CZ20002045A3 (en) | 2000-09-13 |
| EP1036104A1 (en) | 2000-09-20 |
| HRP20000369A2 (en) | 2001-04-30 |
| DE19753723A1 (en) | 1999-06-10 |
| PT1036104E (en) | 2003-01-31 |
| AR016974A1 (en) | 2001-08-01 |
| PL340692A1 (en) | 2001-02-26 |
| ID25492A (en) | 2000-10-05 |
| WO1999029751A1 (en) | 1999-06-17 |
| ZA9811054B (en) | 1999-06-07 |
| YU34000A (en) | 2002-09-19 |
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