DK146047B - POLYMERIZABLE MATERIALS FOR PREPARING COATS WITH GOOD SPOTTING, SCREAM AND SCRAP FACTOR, AND METHOD OF PRODUCING THEREOF - Google Patents
POLYMERIZABLE MATERIALS FOR PREPARING COATS WITH GOOD SPOTTING, SCREAM AND SCRAP FACTOR, AND METHOD OF PRODUCING THEREOF Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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Description
146047146047
Den foreliggende opfindelse angår et polymeriserbart materiale til fremstilling af overtræk med god plet-, skramme og ridsefasthed og bestående af en eller flere monomerer der er diestere af en diol med en eller to organiske syrer. Opfindelsen angår tillige en fremgangsmåde til fremstilling af det polymeriserbare materiale.The present invention relates to a polymerizable material for preparing coatings having good stain, scratch and scratch resistance and consisting of one or more monomers which are diesters of a diol with one or two organic acids. The invention also relates to a process for preparing the polymerizable material.
Ifølge opfindelsen består det polymeriserbare materiale af (a) mindst én forbindelse med den almene formel R11 CH, CH, R11According to the invention, the polymerizable material consists of (a) at least one compound of the general formula R11 CH, CH, R11
I I 3 I 3 II I 3 I 3 I
ch2=c-co-och2-c-ch2-o-co-c-ch2o-oc-c=ch2 Ich2 = c-co-and2-c-ch2-o-co-c-ch2o-oc-c = ch2 I
ch3 ch3 hvor R11 er et hydrogenatom eller en metylgruppe, og/eller (b) mindst én forbindelse med den almene formel CH, CH, 9 1 3 I 3 lowherein R 11 is a hydrogen atom or a methyl group and / or (b) at least one compound of the general formula CH, CH, 9
R C0~0CH,-C-CEL-0-C0-C-CH-0-0CR IIR C0 ~ 0CH, -C-CEL-0-C0-C-CH-0-0CR II
I II I
CH3 CH3 R11CH3 CH3 R11
9 10 I9 10 I
hvor en af grupperne R og R er en gruppe med formlen -C=CH_ 11 Z hvor R har den ovenfor angivne betydning, og den anden af 9 10 grupperne R og R er en substitueret eller usubstitueret alkyl-, cykloalkyl-, aralkyl- eller arylgruppe, samt eventuelt (c) en eller flere forbindelser med den almene formel CH, CH, 9 · ^ 1 J 10wherein one of the groups R and R is a group of the formula -C = CH_ 11 Z where R is as defined above and the other of the groups R and R is a substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl group, and optionally (c) one or more compounds of the general formula CH, CH, 9 · 1 J 10
R C0-0CHo-C-CH,-0-C0-C-CH,0-0CR IIIR C0-0CHo-C-CH, -0-C0-C-CH, 0-0CR III
2 t 2 ,2 CH3 CH3 9 10 hvor R og R har den ovenfor angivne betydning undtagen en gruppe -C=CH,.2 t 2, 2 CH 3 CH 3 9 10 where R and R have the meaning given above except for a group -C = CH 2.
lulu
RR
Særlig hensigtsmæssigt består ifølge opfindelsen det polymeriserbare materiale af 2,5-35 vægt% af en eller flere 2 146047 forbindelser med formel I, 30-95 vægt% af en eller flere forbindelser med formel II og 2,5-35 vægt% af en eller flere forbindelser med formel III.Particularly advantageously according to the invention, the polymerizable material consists of 2.5-35% by weight of one or more compounds of formula I, 30-95% by weight of one or more compounds of formula II and 2.5-35% by weight of a or more compounds of formula III.
Ifølge opfindelsen fremstiller man det polymeriserbare materiale på den i patentkrav 3 angivne måde. Man omsætter altså hydroxypivalylhydroxypivalat, der har formlen CH- CH, I 3 | 3According to the invention, the polymerizable material is prepared in the manner specified in claim 3. Thus, hydroxypivalyl hydroxypivalate having the formula CH-CH, I 3 is reacted | 3
HOCH-CCH,OCOCCH~OHHOCH-CCH, OCOCCH ~ OH
21 2 j 2 CH3 ch3 med akrylsyre, metakrylsyre eller et syreanhydrid eller syreklorid deraf samt eventuelt tillige med en ikke i sig selv po-lymeriserbar alifatisk, alicyklisk eller aromatisk monofunktionel syre; omsætninger sker ved en temperatur på 50-150°C i nærværelse af en syrekatalysator og eventuelt en inhibitor, og akrylforbindelsen tilsættes gradvis og på en sådan måde at molforholdet mellem den samlede mængde af denne og hydroxypiva-lylhydroxypilat er i området mellem 1,5:1 og 1:5 og molforholdet mellem den samlede syremængde og nævnte diol er i området mellem 2:1 og 10:1.CH 2 CH 3 CH 3 with acrylic acid, methacrylic acid or an acid anhydride or acid chloride thereof, and optionally also with a non-polymerizable aliphatic, alicyclic or aromatic monofunctional acid; Reactions occur at a temperature of 50-150 ° C in the presence of an acid catalyst and optionally an inhibitor, and the acrylic compound is added gradually and in such a way that the molar ratio of the total amount thereof to hydroxypaviolyl hydroxypilate is in the range of 1.5: 1 and 1: 5 and the mole ratio of the total amount of acid to said diol is in the range of 2: 1 to 10: 1.
Den gradvise tilsætning af akrylforbindelsen sker ifølge opfindelsen hensigtsmæssigt ved at man først sætter ca. halvdelen af akrylforbindelsens totale mængde til diolen, hvorpå den resterende mængde deraf tilsættes i løbet af 1/4 til 6 timer. Reaktionsproduktet af hydroxypivalylhydroxypivalatet og akrylforbindelsen er en akrylmonomer som kan polymeriseres ved ioniserende bestråling,med aktinisk lys eller ved anvendelse af friradikal-dannende katalysatorer, og den resulterende polymer er et hårdt, mod skrammer modstandsdygtigt materiale.According to the invention, the gradual addition of the acrylic compound is conveniently done by first adding approx. half of the total amount of the acrylic compound to the diol, then the remaining amount thereof is added over 1/4 to 6 hours. The reaction product of the hydroxypivalyl hydroxypivalate and acrylic compound is an acrylic monomer which can be polymerized by ionizing radiation, with actinic light or by the use of free radical-forming catalysts, and the resulting polymer is a hard, scratch resistant material.
Akrylmonanereme, være sig alene eller sammen med forbindelser II og/eller forbindelser III, er meget strålingsfølsomme. Når de udsættes for lave doser af ioniserende bestråling eller aktinisk lys eller for friradikal-dannende katalysatorer, polymeriserer de til ekstremt stærkt og plet-modstandsdygtigt materiale. Disse hærdede materialer har fortrinlig modstandsdygtighed ved strenge pletforsøg og er modstandsdygtige mod 146047 3 ridser og skrammer.The acrylic monanes, alone or together with compounds II and / or compounds III, are highly radiation sensitive. When exposed to low doses of ionizing radiation or actinic light or to free radical-forming catalysts, they polymerize to extremely strong and stain resistant material. These hardened materials have excellent resistance to severe stain tests and are resistant to scratches and scratches.
Fra britisk patentskrift nr. 1.135.647 kendes der estere af trimetyl-1,6-hexandiol med α,β-umættede alifatiske monokarboxylsyrer med fortrinsvis 3-6 C-atomer og især akryl-, metakryl- eller krotonsyre samt eventuelt en mættet alifatisk Cl-18 monofcerboxylsyre. Forbindelserne skal bruges som smøreolieadditiver eller monomerer ved homo- eller copolymerisa-tion. Skriftet siger ikke rigtig noget om hvad de herved frembragte polymerer kan bruges til, men det synes ikke at være overtræk, i hvert fald ikke overtræk der hærdes og polymeriseres in situ på det underlag, overtrækket skal dannes på, sådan som det her foreliggende polymeriserbare materiale.British Patent No. 1,135,647 discloses esters of trimethyl-1,6-hexanediol with α, β-unsaturated aliphatic monocarboxylic acids having preferably 3-6C atoms and especially acrylic, methacrylic or crotonic acid and optionally a saturated aliphatic C1 -18 monofcerboxylic acid. The compounds should be used as lubricating oil additives or monomers by homo- or copolymerization. The script does not really say what the polymers thus produced can be used for, but it does not appear to be coatings, at least not coatings which are cured and polymerized in situ on the substrate on which the coating is to be formed, such as the present polymerizable material. .
Trimetyl-1,6-hexandiol-diakrylat er ikke en lettilgængelig forbindelse, og her har man derfor foretrukket at lave sammenligningsforsøg mellem 1,6-hexandiol-diakrylat (HDDA) som et rimeligt substitut derfor og dermed repræsentant for kendt teknik, og akryloxypivalylakryloxypivalat (APAP) som repræsentant for den omhandlede monomer med formel, i. Rapport over forsøgene er vist nedenfor, idet også forsøgsteknikken er beskrevet i disse sammenligningsforsøg.Trimethyl-1,6-hexanediol diacrylate is not an readily available compound, and here it is therefore preferred to make comparative experiments between 1,6-hexanediol diacrylate (HDDA) as a reasonable substitute therefor and thus representative of prior art, and acryloxypivalyl acryloxypivalent ( APAP) as representative of the subject monomer of formula, i. Report on the experiments is shown below, the test technique being also described in these comparative experiments.
Sammenligningsforsøg Forsøg 1Comparative Experiment Experiment 1
To overtrækspræparater blev fremstillet af følgende bestanddele:Two coating compositions were prepared from the following ingredients:
Præparat A: 95 vægt% 1,6-hexandiol-diakrylat (HDDA) 5 vægt% isobutylbenzoinæter (IBBI)Preparation A: 95% by weight 1,6-hexanediol diacrylate (HDDA) 5% by weight isobutylbenzoin ether (IBBI)
Præparat B: 95 vægt% akryloxypivalylakryloxypivalat (APAP) 5 vægt% isobutylbenzoinæter (IBBE)Preparation B: 95% by weight acryloxypivalylacryloxypivalate (APAP) 5% by weight isobutylbenzoin ethers (IBBE)
De to præparater påførtes hver for sig på aluminiumpaneler i en tykkelse på ca. 0,025 mm. Et antal således overtrukne paneler førtes én eller tre gange med forskellig fart i luft ind under fire middeltryks ultravioletlysudsendende kviksølvdamplamper der alle arbejdede ved ca. 200 watt/2,54 cm, i en afstand på ca. 7,6 cm. Flere andre af de overtrukne paneler førtes én gang med forskellig fart i nitrogen (oxygenindhold: ca. 15 rumfangsdele oxygen pr. million dele gasblanding) under én middeltryks ultravioletlysudsenden- 4 146047 de kviksølvdamplampe der arbejdede ved ca. 200 watt/2,54 can, i en afstand på ca. 7,6 cm.The two compositions were individually applied to aluminum panels at a thickness of approx. 0.025 mm. A number of panels thus coated were brought once or three times at different speeds into the air under four medium pressure ultraviolet light emitting mercury vapor lamps, all operating at approx. 200 watts / 2.54 cm, at a distance of approx. 7.6 cm. Several other of the coated panels were once passed at different speeds in nitrogen (oxygen content: about 15 volumes of oxygen per million parts of gas mixture) under one medium-pressure ultraviolet light emitter, the mercury vapor lamp operating at approx. 200 watts / 2.54 can, at a distance of approx. 7.6 cm.
Efter behandlingen med ultraviolet lys blev overtrækkene evalueret ved blyants-hårdhedsprøven ved at blive prøvet med følgende sæt blyanter i rækkefølge efter stigende hårdhed: 4B (blødest), 3B, 2B, B, HB, F, H, 2H, 4H, 5H, 6H og 7H (hårdest). Panelerne blev også evalueret med hensyn til overfladehærdning.After the ultraviolet light treatment, the coatings were evaluated by the pencil hardness test by testing the following set of pencils in order of increasing hardness: 4B (softest), 3B, 2B, B, HB, F, H, 2H, 4H, 5H, 6H and 7H (hardest). The panels were also evaluated in terms of surface hardening.
Den fart hvormed panelerne førtes under kviksølvlampen eller -lamperne, den anvendte hærdningsatmosfære og de skete iagttagelser er anført i tabel 1.The speed at which the panels were conducted under the mercury lamp (s), the curing atmosphere used and the observations made are listed in Table 1.
Tabel 1Table 1
Transport- Passa- Blyantshårdhed og overfladehærdning fart, m/min. ger præparat A præparat BTransport- Passa- Pencil hardness and surface hardening speed, m / min. prepares preparation A preparation B
•_95% HDDA 5% IBBE 95% APAP 5% IBBE• _95% HDDA 5% IBBE 95% APAP 5% IBBE
Luft- 6,1 1 H; note 1 2H; note 1 hærdning 8,2 l Ff note 1 H; note 1 9,1 1 Ff note 1 Hf note 1 _6,1_3_4Hf note 2_4H ·, note 2_Air 6.1 L H; note 1 2H; note 1 cure 8.2 l Ff note 1 H; note 1 9.1 1 Ff note 1 Hf note 1 _6,1_3_4Hf note 2_4H ·, note 2_
Nitrogen- 15,2 1 HBf note 2 Hf note 2 hærdning 3o,5 1 4Bf note 3 HBf note 2 45,7 1 4Bf note 3 Bf note 2 _61,0 1 4Bf note 3 4Bf note 4Nitrogen 15.2 1 HBf note 2 Hf note 2 hardening 3o, 5 1 4Bf note 3 HBf note 2 45.7 1 4Bf note 3 Bf note 2 _61.0 1 4Bf note 3 4Bf note 4
Note 1 - Klæbrig, uacceptabel overfladeNote 1 - Sticky, unacceptable surface
Note 2 - Hærdet helt igennem incl. ikke-klæbrig overflade Note 3 - Tør overflade, men utilstrækkelig hærdning af overtrækketf overtrækket kan fjernes med en fingernegl.Note 2 - Cured throughout incl. non-sticky surface Note 3 - Dry surface, but insufficient curing of the coating f The coating can be removed with a fingernail.
Note 4 - Hærdningen er marginalNote 4 - The cure is marginal
Forsøg 2Experiment 2
Der fremstilledes to overtrækspræparater indeholdende følgende bestanddele:Two coating compositions containing the following ingredients were prepared:
Præparat C: Kommercielt harpikspræparat (også indeholdende en fotoigangsætter) udgør 80% af binderen, og 1,6-hexandioldiakrylat (HDDA) udgør 20 vægt% af binderenPreparation C: Commercial resin preparation (also containing a photoengineer) constitutes 80% of the binder, and 1,6-hexanediol diacrylate (HDDA) constitutes 20% by weight of the binder.
Titandioxyd (rutil) - vægtforhold pigment/binder = 0.,5 146047 5Titanium dioxide (rutile) - weight ratio pigment / binder = 0., 5 146047 5
Præparat D: Kommercielt harpikspræparat (også indeholdende en f oto igangsætter) udgørSO vægt% af binderen, og Akryloxypivalylakryloxypivalat udgør 20 vægt% af binderenPreparation D: Commercial resin preparation (also containing a photo initiator) constitutes SO% by weight of the binder, and Acryloxypivalylacryloxypivalate constitutes 20% by weight of the binder
Titandioxyd (rutil) - vægtforhold pigment/binder = 0,5Titanium dioxide (rutile) - pigment / binder weight ratio = 0.5
Harpiksen og fotoigangsætteren og de relative mængder deraf var ens i begge de to præparater C og D. De to præparater blev påført som overtræk på paneler på en sådan måde at tykkelsen af overtrækket efter hærdning ville være i området 0,038-0,051 mm. Alle de med overtrækket forsynede paneler førtes et antal gange i luft under middeltryks ultravioletlysudsendende kviksølvdamplamper der alle arbejdede med ca. 200 watt/2,54 cm, og i en afstand på ca.The resin and photoiganger and their relative amounts were similar in both the two compositions C and D. The two compositions were applied as coatings to panels in such a way that the thickness of the coating after curing would be in the range of 0.038-0.051 mm. All of the coated panels were airborne a number of times under medium-pressure ultraviolet light-emitting mercury vapor lamps, all working with approx. 200 watts / 2.54 cm, and at a distance of approx.
7,6 cm, i henhold til følgende skema: én passage med 24,4 m pr. minut, to passager med 12,2 m pr. minut og to passager med 6,1 m pr. minut.7.6 cm, according to the following diagram: one passage with 24.4 m per square meter. per minute, two passes at 12.2 m per minute. per minute and two passages with 6.1 m per minute. minute.
Derefter måltes 60° glansen af alle de således behandlede paneler. Resultaterne er anført i tabel 2.Then the 60 ° gloss of all panels thus treated was measured. The results are listed in Table 2.
Tabel 2Table 2
Overtrækspræparat 60° glans, pct.Coating composition 60 ° gloss, per cent.
C 95 D 99+C 95 D 99+
Panelerne blev udsat for vejrpåvirkning i et udendørs anlæg i Ft. Lauderdale, Florida, USA, i 15 måneder. Herunder blev 60° glansen målt med mellemrum og den procentuelle bevarelse af den oprindelige 60° glans blev bestemt. Tidsmellemrummene og resultaterne fremgår af tabel 3.The panels were exposed to weather in an outdoor facility in Ft. Lauderdale, Florida, USA, for 15 months. Below, the 60 ° gloss was measured at intervals and the percentage retention of the original 60 ° gloss was determined. The time intervals and results are shown in Table 3.
Tabel 3Table 3
Overtræks- Bevarelse af 60° glans, pct. af oprindelig 60° glans præparat efter 3 efter 6 efter 9 efter 12 efter 15 _måneder måneder måneder måneder måneder_ C 68 49 26 13 7 D 79 65 44 25 30 6 146047Coating- Preservation of 60 ° gloss, per cent. of original 60 ° gloss preparation after 3 after 6 after 9 after 12 after 15 _ months months months months months_ C 68 49 26 13 7 D 79 65 44 25 30 6 146047
De i de to sammenligningsforsøg viste resultater viser at oxygen har tendens til at inhibere hærdning af overfladen af APAP. Det skal i denne forbindelse bemærkes at blyantshårdhedsprøven er et mål for graden af hærdning af overtrækkets indre. Det er ikke et mål for graden af hærdning af overtrækkets overflade. Det første sammenligningsforsøg belyser dette forhold.The results shown in the two comparison experiments show that oxygen tends to inhibit surface curing of APAP. In this connection, it should be noted that the pencil hardness test is a measure of the degree of curing of the interior of the coating. It is not a measure of the degree of curing of the coating surface. The first comparison experiment illustrates this relationship.
I tabel 1, hvor HDDA og APAP blev udsat for ultraviolet lys fra fire kviksølvdamplamper i luft ved én passage var blyantshårdheden for APAP stedse større end for HDDA. I alle tilfælde hvor der brugtes én passage hærdede overfladen ikke tilstrækkeligt på grund af oxygeninhibering. Bemærk at blyantshårdheden gik ned når transportørens fart steg. Det fordrede tre passager med den laveste transporthastighed at give en 4h blyantshårdhed og en ikke-klæbrig overflade, når behandlingen skete i luft. Dette er omtrent det samme som eksponering til fire lamper ved en passage med en fart på 2 m/min. De anførte data viser (1) at APAP er bedre end HDDA, (2) at begge systemer kan have rimelig indre hårdhed selv om overfladen er uacceptabelt hærdet og (3) at oxygeninhibering kan overvindes ved massiv eksponering til ultraviolet bestråling. En blyantshårdhed på H eller 2H er acceptabel til de fleste anvendelser.In Table 1, where HDDA and APAP were exposed to ultraviolet light from four mercury vapor lamps in air at one pass, the pencil hardness of APAP was consistently greater than that of HDDA. In all cases where one passage was used, the surface did not cure sufficiently due to oxygen inhibition. Note that the pencil hardness went down as the carrier speed increased. It required three passes with the lowest transport speed to provide a 4h pencil hardness and a non-sticky surface when the treatment was done in air. This is about the same as exposure to four lamps at a speed of 2 m / min. The data cited show (1) that APAP is better than HDDA, (2) that both systems can have reasonable internal hardness even though the surface is unacceptably hardened, and (3) that oxygen inhibition can be overcome by massive exposure to ultraviolet radiation. A pencil hardness of H or 2H is acceptable for most applications.
De i tabel 1 viste data viser tillige at APAP er bedre end HDDA ved eksponering til ultraviolet bestråling fra én lampe i nitrogen. Da der ikke var signifikante mængder oxygen til stede, var oxygeninhibering af overfladehærdningen ikke en faktor her. De angivne data viser at blyantshårdheden går ned efterhånden som transportørens fart stiger. Det ses også at der kan bruges større transporthastigheder og færre lamper i nitrogen end i luft. Det viser naturligvis at der behøves mindre ultraviolet bestråling i nitrogen end i luft.The data shown in Table 1 also shows that APAP is better than HDDA in exposure to ultraviolet radiation from one lamp in nitrogen. As no significant amounts of oxygen were present, oxygen inhibition of the surface cure was not a factor here. The data provided shows that the pencil hardness decreases as the carrier speed increases. It is also seen that larger transport speeds and fewer lamps can be used in nitrogen than in air. Of course, this shows that less ultraviolet radiation is needed in nitrogen than in air.
APAPs overlegenhed over HDDA fremgår også af det andet forsøg. De her anførte testdata viser (1) at den oprindelige glans af præparatet indeholdende APAP var større end glansen af præparatet med HDDA, og (2) at præparatet med APAP bevarede glansen meget bedre end præparatet med HDDA.APAP's superiority over HDDA is also evident in the second trial. The test data presented here shows (1) that the original luster of the preparation containing APAP was greater than the luster of the preparation with HDDA, and (2) that the preparation with APAP retained its luster much better than the composition with HDDA.
U® 047 7U® 047 7
Udførlig beskrivelse af opfindelsenDetailed description of the invention
Omsætningen mellem diolen og akrylforbindelsen sker som nævnt ved 50-150°C, fortrinsvis 95-100°C. Det molære forhold mellem samlet syremængde og diol er som nævnt mellem 2:1 og 10:1, fortrinsvis således at der anvendes 2-2,5 mol sur komponent pr. mol diol.The reaction between the diol and the acrylic compound occurs as mentioned at 50-150 ° C, preferably 95-100 ° C. The molar ratio of total acid to diol is, as mentioned, between 2: 1 and 10: 1, preferably such that 2-2.5 moles of acidic component is used per day. mol diol.
Som syrekatalysator kan der fx bruges svovlsyre, p-tolu-ensulfonsyre, fosforsyre og/eller hydrogenklorid. Katalysatoren er sædvanligvis til stede i en mængde på 0,1-5 vægt% af reaktionsdeltagerne .As an acid catalyst, for example, sulfuric acid, p-toluenesulfonic acid, phosphoric acid and / or hydrogen chloride can be used. The catalyst is usually present in an amount of 0.1-5% by weight of the reaction participants.
I de fleste tilfælde anvendes der tillige en friradikal-dannende inhibitor for at forhindre reaktionsdeltagerne i at stivne. Der kan anvendes enhver konventionel friradikal-dannende inhibitor, fx hydroquinon, metylquinon eller p-metoxyfenol. In- . hibitoren er sædvanligvis til stede i en vægtmængde på 0,1-5 vægt% af reaktionsdeltagerne.In most cases, a free radical-forming inhibitor is also used to prevent the reaction participants from solidifying. Any conventional free radical-forming inhibitor, e.g., hydroquinone, methylquinone or p-methoxyphenol, may be used. In-. the hibitor is usually present in a weight range of 0.1-5% by weight of the reaction participants.
Reaktionen indledes ved at der til diolen sættes en del af akrylforbindelsen, katalysatoren og inhibitoren og opvarmes.The reaction is initiated by adding to the diol a portion of the acrylic compound, catalyst and inhibitor and heating.
Som nævnt er det ønskeligt at den sure komponent sættes gradvis til blandingen, fx så der tilsættes indtil ca. 50% af den totale mængde af den sure bestanddel sammen med diolen, mens resten så tilsættes i løbet af fx 1/4 til 6 timer, fordelagtigt dråbevis .As mentioned, it is desirable that the acidic component is added gradually to the mixture, e.g. 50% of the total amount of the acidic component together with the diol, while the remainder is then added over eg 1/4 to 6 hours, advantageously dropwise.
Det har vist sig, at hvis den sure komponent ikke tilsættes gradvis, er der en tendens til polymerisatdannelse i reaktionsblandingen, hvorved udbyttet af den ønskede forbindelse nedsættes væsentligt. Det apparat, hvori reaktionen foregår, forurenes endvidere med polymer, og det er vanskeligt at rense reaktionsproduktet. Hvis akrylforbindelsen tilsættes på en gang bliver monomerudbyttet langt lavere end ved ovennævnte metode. Eventuelt kan der anvendes et opløsningsmiddel til dannelse af en azeotrop blanding med det vand, der fremkommer ved omsætningen. Herved opnås at reaktionen lettere fuldføres. Der kan anvendes ethvert alifatisk, cykloalifatisk eller aromatisk kulbrinteopløsningsmiddel. Eksempler på særligt egnede opløsningsmidler er hexan, pentan, cyklopentan, cyklohexan, benzen, toluen og xylen og blandinger af disse. Særlig foretrækkes cyklohexan.It has been found that if the acidic component is not added gradually, there is a tendency for polymerization in the reaction mixture, thereby substantially reducing the yield of the desired compound. Furthermore, the apparatus in which the reaction takes place is contaminated with polymer and it is difficult to purify the reaction product. If the acrylic compound is added at once, the monomer yield becomes much lower than by the above method. Optionally, a solvent may be used to form an azeotropic mixture with the water resulting from the reaction. Hereby the reaction is more easily completed. Any aliphatic, cycloaliphatic or aromatic hydrocarbon solvent may be used. Examples of particularly suitable solvents are hexane, pentane, cyclopentane, cyclohexane, benzene, toluene and xylene and mixtures thereof. Cyclohexane is particularly preferred.
8 1460678 146067
Hvis der anvendes et opløsningsmiddel, indeholder reaktionsblandingen med fordel 1-60 vægt% deraf.If a solvent is used, the reaction mixture advantageously contains 1-60% by weight thereof.
De omhandlede forbindelser med formel 1 kan med eller uden tilstedeværelse af forbindelser II og III, homopolymeri-seres i nærværelse af friradikaldannende katalysatorer eller ved bestråling, eller kan copolymeriseres med andre monomerer såsom akrylmonomerer, fx alkylakrylater og alkylmetakrylater, eller kan tilsættes til andre polymerer og anvendes i form af blandinger der hærdes sammen. Eksempler på polymerer som kan blandes med de omhandlede akrylmonomerer er polyalkylakrylater såsom polyætylakrylat, poly-(2-ætylhexylakrylat) og poly-butylakrylat til dannelse af mere bøjelige produkter, samt vinylpolymerer og -copolymerer såsom vinylklorid-vinylacetatcopo-lymerer, ligeledes til dannelse af mere bøjelige produkter. Cellulosepolymerer såsom celluloseacetatbutyrat (viskositet 0,5 sek.) kan hærdes sammen med de omhandlede akrylmonomerer til forøgelse af de resulterende produkters smidighed. Forbindelserne kan således blandes med andre monomerer eller polymerer, og blandingen kan derefter hærdes enten under anvendelse af peroxyd eller ved at udsætte blandingen for aktinisk eller ionisk bestråling.The present compounds of formula 1 may, with or without the presence of compounds II and III, be homopolymerized in the presence of free radical-forming catalysts or by irradiation, or may be copolymerized with other monomers such as acrylic monomers, e.g., alkyl acrylates and alkyl methacrylates, or may be added to other polymers and is used in the form of mixtures which cure together. Examples of polymers which can be blended with the acrylic monomers of the present invention are polyalkyl acrylates such as polyethyl acrylate, poly (2-ethylhexyl acrylate) and polybutyl acrylate to form more flexible products, and vinyl polymers and copolymers such as vinyl chloride-vinyl acetate copolymer flexible products. Cellulose polymers such as cellulose acetate butyrate (viscosity 0.5 sec) can be cured together with the acrylic monomers concerned to increase the flexibility of the resulting products. Thus, the compounds can be mixed with other monomers or polymers and the mixture can then be cured either using peroxide or by subjecting the mixture to actinic or ionic radiation.
Et særligt bøjeligt produkt dannes når der indgår en ikke i sig selv polymeriserbar monofunktionel alifatisk, alicyklisk eller aromatisk syre i reaktionsblandingen med diolen og akrylforbindelsen, så der sker copolymerisation af den fremstillede monomerblanding ved bestråling med aktinisk lys eller ioniserende stråling eller behandling med en friradikal katalysator. De dannede polymerer, der bliver mere bøjelige, har tillige forbed-. ret adhæsion til mange materialer.A particularly flexible product is formed when a non-polymerizable monofunctional aliphatic, alicyclic or aromatic acid is included in the reaction mixture with the diol and acrylic compound, so that the monomer mixture produced is copolymerized by irradiation with actinic light or ionizing radiation or treating with a freezing radiator. . The polymers formed, which become more flexible, have also improved. right adhesion to many materials.
Der kan anvendes enhver ikke-polymeriserbar, monofunktionel alifatisk, alicyklisk eller aromatisk syre til omsætning med diolen og akrylforbindelsen. Denne syre er ikke selv polymeriserbar. Eksempler på sådanne syrer er eddikesyre, smørsyre, benzoesyre, propionsyre, kapronsyre, 2-ætylhexansyre, oktansyre, .laurinsyre, stearinsyre, neosyrer såsom neodekansyre, oliesyre, cyklohexankarboxylsyre, p-metylbenzoesyre, p-metoxybenzoesyre, p-nitrobenzoesyre, p-klorbenzoesyre, kloreddikesyre, triklor-eddikesyre og aminoeddikesyre, samt deres anhydrider. De fore- 146047 9 trukne ikke-polymeriserbare syrer er eddikesyre, butyrsyre, 2-ætylhexansyre og benzoesyre.Any non-polymerizable, monofunctional aliphatic, alicyclic or aromatic acid may be used to react with the diol and acrylic compound. This acid is not itself polymerizable. Examples of such acids are acetic acid, butyric acid, benzoic acid, propionic acid, capric acid, 2-ethylhexanoic acid, octanoic acid, lauric acid, stearic acid, neo acids such as neodecanoic acid, oleic acid, cyclohexanecarboxylic acid, p-methylbenzoic acid, p-methoxybenzoic acid, p-methoxybenzoic acid chloroacetic acid, trichloroacetic acid and aminoacetic acid, as well as their anhydrides. The preferred non-polymerizable acids are acetic acid, butyric acid, 2-ethylhexanoic acid and benzoic acid.
Molforholdet mdilem akrylforbindelsen og diolen kan variere meget, men er sædvanligvis mellem 1,5:1 og 1:5. Det foretrækkes at anvende 1,5-0,75 mol akrylforbindelse pr. mol diol.The mole ratio between the acrylic compound and the diol can vary widely, but is usually between 1.5: 1 and 1: 5. It is preferred to use 1.5-0.75 moles of acrylic compound per day. mol diol.
Den resterende del af den sure komponent er den ikke-polymeriserbare (alifatiske, alicykliske eller aromatiske) syre, der tilsættes som allerede nævnt i en sådan mængde at molforholdet mellem total syremængde og hydroxypivalylhydroxypivalat er mellem 2:1 og 10:1, fortrinsvis mellem 2,0 og 2,4 mol total syre pr. mol diol.The remaining portion of the acidic component is the non-polymerizable (aliphatic, alicyclic or aromatic) acid which is added as already mentioned in such an amount that the mole ratio of total acid amount to hydroxypivalyl hydroxypivalate is between 2: 1 and 10: 1, preferably between 2 , 0 and 2.4 moles total acid per mol diol.
Monomerer med formel I kan polymeriseres ved bestråling, fordi de er ekstremt strålingsfølsomme. Strålingsfølsomme monomerer er vanskelige at fremstille, og det er vanskeligt at forudsige hvilke monomerer der har denne egenskab. Med udtrykket "bestråling" menes i nærværende beskrivelse høj energistråling og/ eller den sekundære energistråling, der stammer fra omdannelsen af elektroner eller andre partikelenergier til røntgenstråler eller gammastråler. Selv om der kan anvendes forskellige strålingskilder til det ønskede formål, såsom røntgenstråler og gammastråler, har stråling tilvejebragt ved hjælp af accelererende højenergielektroner vist sig at være meget velegnet og økonomisk i brug samtidig med at der opnås meget tilfredsstillende resultater. Imidlertid kan der anvendes enhver stråling uafhængig af strålingsarten og anvendt apparattype, når blot den ioniserende stråling er ækvivalent med mindst ca. 100.000 elektronvolt .Monomers of formula I can be polymerized by irradiation because they are extremely radiation sensitive. Radiation-sensitive monomers are difficult to prepare, and it is difficult to predict which monomers have this property. As used herein, the term "radiation" means high energy radiation and / or secondary energy radiation resulting from the conversion of electrons or other particle energies to X-rays or gamma rays. Although various radiation sources can be used for the desired purpose, such as X-rays and gamma rays, radiation provided by accelerating high-energy electrons has proved to be very suitable and economical in use while achieving very satisfactory results. However, any radiation irrespective of the radiation type and type of apparatus used can be used, provided that the ionizing radiation is equivalent to at least approx. 100,000 electron volts.
Der er ingen øvre grænse for den tilførte elektronenergi, men den ønskede effekt kan i praksis opnås uden at man overstiger 20.000.000 elektronvolt. I almindelighed er indtrængningsdybden i det til behandling værende massive materiale desto større jo højere elektronenergi der anvendes. Ved andre strålingstyper, fx gamma- og røntgenstråler, er det ønskeligt med energisystemer der er ækvivalente med ovennævnte elektronvoltområde .There is no upper limit to the electron energy supplied, but the desired effect can be achieved in practice without exceeding 20,000,000 electron volts. In general, the depth of penetration of the solid material under consideration is greater the higher the electron energy used. For other types of radiation, for example gamma and X-rays, energy systems equivalent to the above-mentioned electron-volt region are desirable.
Udtrykket "bestråling" omfatter ioniserende stråling og defineres som stråling indeholdende energi der mindst er 10 148047 tilstrækkelig til at producere ioner eller til at nedbryde kemiske bindinger; det omfatter således også stråling som ioniserende partikelstråling samt stråling af den type der betegnes "ioniserende elektromagnetisk stråling".The term "radiation" encompasses ionizing radiation and is defined as radiation containing energy at least sufficient to produce ions or to break down chemical bonds; it thus also includes radiation such as ionizing particle radiation as well as radiation of the type termed "ionizing electromagnetic radiation".
Udtrykket "ioniserende partikelstråling" anvendes for at betegne elektronudsendelser eller udsendelse af højt accelererende nukleære partikler såsom protoner, neutroner, α-partikler, deutroner og β-partikler eller analoger dertil, der dirigeres således at partiklen projiceres ind i den masse der skal bestråles. Ladede partikler kan accelereres ved hjælp af en elektrisk spændingsforskel ved hjælp af acceleratorer med resonanskamre, van der Graaf generatorer, betatroner, synkro-troner, cyklotroner etc. Neutronudsendelse kan ske ved bombardering af et letmetal såsom beryllium med positive partikler med høj energi. Partikeludsendelse kan også opnås ved anvendelse af atommiler, radioaktive isotoper eller andre naturlige eller syntetiske radioaktive materialer.The term "ionizing particle radiation" is used to denote electron emitted or emitted by highly accelerating nuclear particles such as protons, neutrons, α-particles, deutrons and β-particles or analogs thereof, which are directed so as to project the particle into the mass to be irradiated. Charged particles can be accelerated by means of an electrical voltage difference by means of accelerators with resonant chambers, van der Graaf generators, betatrons, synchro- trons, cyclotrons, etc. Neutron emission can be achieved by bombarding a light metal such as beryllium with high-energy positive particles. Particle emission can also be achieved by using atomic miles, radioactive isotopes or other natural or synthetic radioactive materials.
Ioniserende elektronisk bestråling frembringes når en metalskydeskive, fx af wolfram, bombarderes med elektroner med passende energiindhold. Denne energi tildeles elektronerne ved hjælp af potentielle acceleratorer på over 0,1 million elektronvolt (mev.). Foruden selektiv bestråling, der almindeligvis kaldes røntgenstråling, er ioniserende elektromagnetisk bestråling opnået ved hjælp af en atomreaktor (mile) eller under anvendelse af naturlige eller syntetiske radioaktive stoffer, fx. kobolt 60.Ionizing electronic radiation is produced when a metal cloud disk, e.g., of tungsten, is bombarded with electrons of appropriate energy content. This energy is allocated to the electrons by potential accelerators exceeding 0.1 million electron volts (m.s.). In addition to selective radiation, commonly called X-ray radiation, ionizing electromagnetic radiation is obtained by means of a nuclear reactor (mile) or using natural or synthetic radioactive substances, e.g. cobalt 60.
I handelen findes forskellige typer lineære acceleratorer for elektroner der har stor kraf, fx "ARCO" ® -acceleratorer af den fremadskridende bølgeacceleratortype, model Mark I, der virker ved 3-10 millioner elektronvolt, og leveres af High Voltage Engineering Corporation, Burlington, Massachusetts, eller andre acceleratortyper beskrevet i US patentskrift nr. 2.763.609 og GB patentskrift nr. 762.953.In the trade, there are various types of high-power linear accelerators, for example, "ARCO" ® accelerating wave accelerator type Model Mark I, operating at 3-10 million electron volts, and supplied by the High Voltage Engineering Corporation, Burlington, Massachusetts. , or other accelerator types disclosed in U.S. Patent No. 2,763,609 and GB Patent No. 762,953.
De omhandlede monomerer polymeriseres ved enhver total strålingsdosis på mellem 0,2 megarad og 20 megarad. En rad defineres som den mængde stråling, der kræves for at tilføre 100 g erg pr. g materiale der behandles, og en megarad er 10 rad.The subject monomers are polymerized at any total radiation dose of between 0.2 megarad and 20 megarad. A row is defined as the amount of radiation required to supply 100 g of erg per g of material being processed and a megarad is 10 rad.
146047 11146047 11
Den totale strålingsdosis er den totale mængde af bestråling der optages af monomeren. Det har vist sig, at de omhandlede monomerer polymeriseres til hårde, mod skrammer og pletter modstandsdygtige film under anvendelse af en total strålingsdosis på under 4 megarad. Den foretrukne strålingsdosis er mellem 0,5 og 10 megarad.The total radiation dose is the total amount of radiation absorbed by the monomer. It has been found that the present monomers are polymerized into hard, scratch and stain resistant films using a total radiation dose of less than 4 megarads. The preferred radiation dose is between 0.5 and 10 megarad.
De omhandlede monomerer eller blandinger af dem kan også polymeriseres og hærdes ved en fri radikal-mekanisme, hvor der tilsættes friradikal-dannende katalysatorer og monomeren opvarmes til polymerisation. Der kan anvendes enhver konventionel friradikal-dannende katalysator, fx organiske peroxyder eller hydroperoxyder eller estere heraf. Eksempler er benzoyl-peroxyd, tert.-butylperbenzoat, tert.-butylhydroperoxyd, kumen-hydroperoxyd og azobis-(isobutyronitril). Katalysatoren anvendes sædvanligvis i en mængde på 0,1-5 vægt% af monomeren eller af monomerblandingen.The subject monomers or mixtures thereof may also be polymerized and cured by a free radical mechanism where free-radical-forming catalysts are added and the monomer is heated for polymerization. Any conventional free radical-forming catalyst can be used, for example organic peroxides or hydroperoxides or esters thereof. Examples are benzoyl peroxide, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide and azobis (isobutyronitrile). The catalyst is usually used in an amount of 0.1-5% by weight of the monomer or of the monomer mixture.
Monomeren og katalysatoren opvarmes til hærdning. Hærdningstemperaturen varierer fra monomer til monomer, men der anvendes sædvanligvis temperaturer på 24-150°C.The monomer and catalyst are heated to cure. The curing temperature varies from monomer to monomer, but temperatures of 24-150 ° C are usually used.
I mange tilfælde er det ønskeligt at polymerisere uden tilførsel af ydre varme, i hvilke tilfælde der normalt i stedet sættes en accelerator til systemet. Egnede acceleratorer er koboltsalte såsom koboltoktoat og koboltnaftenat, og amin-acceleratorer såsom Ν,Ν-dimetylanilin, N-ætyl-N-hydroxyætyl-m-ætylanilin og N-propyl-N-hydroxyætyl-m-metylanilin.In many cases, it is desirable to polymerize without the application of external heat, in which case an accelerator is usually added to the system instead. Suitable accelerators are cobalt salts such as cobalt octoate and cobalt naphthenate, and amine accelerators such as Ν, Ν-dimethylaniline, N-ethyl-N-hydroxyethyl-m-ethylaniline and N-propyl-N-hydroxyethyl-m-methylaniline.
De omhandlede akrylmonomerer kan også hærdes sammen med andre copolymeriserbare ætylenisk umættede monomere eller med polymert materiale under anvendelse af de ovenfor beskrevne frie radikaldannende katalysatorer.The present acrylic monomers can also be cured together with other copolymerizable ethylenically unsaturated monomers or with polymeric material using the free radical-forming catalysts described above.
Polymerer og copolymerer fremstillet ved polymerisation af de omhandlede monomerer er generelt meget anvendelige som overtræk. De kan således anvendes som beskyttende overtræk for træ til dannelse af vægpaneler, som overtræk for plastmaterialer til dannelse af gulvfliser og som overtræk på metaller såsom aluminium og stål, og disse overtræksmaterialer har den fordel at de ikke let plettes, er resistente mod ridser og skrammer, er vejrbestandige og har kemisk resistens over for syrer og baser. Ved hærdningen fremkommer der tværbinding i stor udstræk- 146047 12 ning i polymerisatet. Overtrækkene er også relativt fleksible, især hvis der ved polymerisatets fremstilling er anvendt en ikke-polymeriserbar syre og er i stand til at danne en stærk binding til forskellige materialer.Polymers and copolymers made by polymerization of the present monomers are generally very useful as coatings. Thus, they can be used as protective coatings for wood to form wall panels, as coatings for plastic materials to form floor tiles and as coatings on metals such as aluminum and steel, and these coatings have the advantage of not being easily stained, scratch-resistant and scratch-resistant. , are weather resistant and have chemical resistance to acids and bases. Upon curing, crosslinking occurs extensively in the polymer. The coatings are also relatively flexible, especially if a non-polymerizable acid is used in the preparation of the polymer and is capable of forming a strong bond to various materials.
Overtrækket kan dannes ved at monomeren påføres på materialet der skal overtrækkes på konventionel måde, fx under anvendelse af valser, "curtain coating", påstrygning og på-sprøjtning. Det overtrukne materiale hærdes derefter enten ved tilsætning af peroxyd til overtrækket eller ved at det udsættes for aktinisk lys eller ioniserende bestråling. Mange af monomererne har ekstremt lav viskositet, således at det er let at påføre produktet ved overtrækning af et materiale.The coating can be formed by applying the monomer to the material to be coated in a conventional manner, for example using rollers, curtain coating, coating and spraying. The coated material is then cured either by the addition of peroxide to the coating or by exposure to actinic light or ionizing radiation. Many of the monomers have extremely low viscosity, so that the product is easily applied by coating a material.
Polymerisation af det omhandlede polymeriserbare materiale med ioniserende bestråling foretrækkes, da den herved foregår ekstremt hurtigt, det tidsrøvende sammenbagningstrin undgås og der ikke kræves opvarmning, hvorved faren for højtemperaturbeskadigelse af varmefølsomme materialer undgås. Der undgås også anvendelse af opløsningsmidler og dermed risiko for giftige og/eller eksplosive opløsningsmiddeldampe. Endelig er polymerisationsovertrækket dannet under anvendelse af ioniserende bestråling tværbundet i højere grad og derfor stærkere end overtræk hærdet på konventionel måde.Polymerization of the subject polymerizable material with ionizing radiation is preferred as it is extremely fast, avoiding the time-consuming baking step and no heating required, thereby avoiding the danger of high temperature damage to heat sensitive materials. Solvents are also avoided and thus the risk of toxic and / or explosive solvent vapors. Finally, the polymerization coating formed using ionizing radiation is more cross-linked and therefore stronger than the coating cured in a conventional manner.
Fremgangsmåden ifølge opfindelsen skal forklares nærmere ved hjælp af de følgende udførelseseksempler.The method according to the invention will be explained in more detail by means of the following exemplary embodiments.
Eksempel 1Example 1
Der fremstilles en akrylmonomer på følgende måde: I en reaktor anbringes 7140 g hydroxypivalylhydroxypi-valat med den i krav 3 viste formel, 1190 g cyklohexan, 1324 g akrylsyre, 62,2 g svovlsyre og 124,4 g hydroquinon. Reaktionsdeltagerne opvarmes under tilbagesvaling ved 94°C, og der tilsættes dråbevis 3972 g akrylsyre i løbet af 30 minutter ved 98°C. Omsætningen foregår i yderligere 4 timer, i hvilket tidsrum der tilsættes 2730 g cyklohexan, og der afdestilleres 1235 g vand. Akryloxypivalylakryloxypivalat opnås i et udbytte på 90 vægt% efter rensning ved vaskning.An acrylic monomer is prepared as follows: Into a reactor is placed 7140 g of hydroxypivalyl hydroxypipalate of the formula shown in claim 3, 1190 g of cyclohexane, 1324 g of acrylic acid, 62.2 g of sulfuric acid and 124.4 g of hydroquinone. The reaction participants are heated at reflux at 94 ° C and 3972 g of acrylic acid are added dropwise over 30 minutes at 98 ° C. The reaction takes place for a further 4 hours, during which time 2730 g of cyclohexane is added and 1235 g of water is distilled off. Acryloxypivalyl acryloxypivalate is obtained in a yield of 90% by weight after purification by washing.
Eksempel 2 13 14 6 Ο Λ 7Example 2 13 14 6 Ο Λ 7
Der fremstilles en strålingsfølsom monomer på følgende måde:A radiation-sensitive monomer is prepared as follows:
Der anbringes 204 g hydroxypivalylhydroxypivalat, 47,4 g metakrylsyre, 3,9 g hydroquinon, 1,9 g svovlsyre og 50 g cyklo-hexan i en reaktionsbeholder. Reaktionsdeltagerne opvarmes under tilbagesvaling til 100°C og der tilsættes dråbevis 142,1 g metakrylsyre i løbet af 35 minutter. Omsætningen foregår i yderligere 3 4 1/2 time, i hvilket tidsrum der tilsættes 100 cm cyklohexan og afdestilleredes 28,6 g vand. Metakryloxypivalylmetakryloxy-pivalat vindes efter rensning.204 g of hydroxypivalyl hydroxypivalate, 47.4 g of methacrylic acid, 3.9 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated to reflux to 100 ° C and 142.1 g of methacrylic acid are added dropwise over 35 minutes. The reaction takes place for a further 3 1/2 hours, during which time 100 cm of cyclohexane is added and 28.6 g of water is distilled off. Methacryloxypivalyl methacryloxy pivalate is recovered after purification.
Eksempel 3Example 3
Der fremstilles en strålingsfølsom monomer på følgende måde:A radiation-sensitive monomer is prepared as follows:
Der anbringes 204 g hydroxypivalylhydroxypivalat, 19,8 g akrylsyre, 23,7 g metakrylsyre, 3,8 g hydroquinon, 1,9 g svovlsyre og 50 g cyklohexan i en reaktionsbeholder. Reaktionsdeltagerne opvarmes til 99°C,og der tilsættes dråbevis 59,5 g akrylsyre og 71,1 g metakrylsyre i løbet af 30 minutter. Omsætningen fortsættes i 5 timer, i løbet af hvilket tidsrum der tilsættes 3 85 cm cyklohexan og opsamledes 34,5 g vand. Det resulterende akrylat-metakrylat isoleres og renses på samme måde som beskrevet i eksempel 1 og 2.204 g of hydroxypivalyl hydroxypivalate, 19.8 g of acrylic acid, 23.7 g of methacrylic acid, 3.8 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated to 99 ° C and 59.5 g of acrylic acid and 71.1 g of methacrylic acid are added dropwise over 30 minutes. The reaction is continued for 5 hours, during which time 3 85 cm of cyclohexane is added and 34.5 g of water are collected. The resulting acrylate methacrylate is isolated and purified in the same manner as described in Examples 1 and 2.
Eksempel 4Example 4
Der anbringes 204 g hydroxypivalylhydroxypivalat, 33 g eddikesyre, 3,6 g hydroquionon, 1,8 g svovlsyre og 50 g cyklohexan i en reaktionsbeholder. Reaktionsdeltagerne opvarmes under tilbagesvaling til 96°C i 1 time og der tilsættes dråbevis 118,9 g akrylsyre i løbet af en 1/2 time ved 97°C. Omsætningen fortsættes ved 97°C i yderligere 4 1/2 time, i hvilket tidsrum der tilsæt- 3 tes 70 cm cyklohexan og 30 g vand afdestilleres. Den resulterende monomer opnås i et udbytte på 92 vægt% efter rensning ved vaskning. Den har hydroxytal 11,93 og Gardner-Holdt-viskositet A-.204 g of hydroxypivalyl hydroxypivalate, 33 g of acetic acid, 3.6 g of hydroquionone, 1.8 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated at reflux to 96 ° C for 1 hour and 118.9 g of acrylic acid are added dropwise over a 1/2 hour at 97 ° C. The reaction is continued at 97 ° C for an additional 4 1/2 hours, during which time 70 cm of cyclohexane and 30 g of water are distilled off. The resulting monomer is obtained in a 92 wt% yield after purification by washing. It has hydroxytal number 11.93 and Gardner-Holdt viscosity A-.
Eksempel 5 14 146047Example 5 14 146047
Der anbringes 204 g hydroxypivalylhydroxypivalat, 34,3 g benzoesyre, 4,2 g hydroquinon, 2,1 g svovlsyre og 50 g cyklohexan i en reaktionsbeholder. Reaktionsblandingen opvarmes til 100°C i 5 timer og 40 minutter. Der tilsættes derefter dråbevis 79.3 g akrylsyre i løbet af 20 minutter ved 97°C til reaktionsblandingen. Reaktionen fortsættes ved 96°C i yderligere 4 1/2 3 time. I løbet af reaktionen tilsættes 120 cm cyklohexan og bortdestilleres 35,0 g vand. Den resulterende monomer opnås i et udbytte på 86,3 vægt% efter rensning ved vask. Produktet har neutralt syretal, hydroxytal 31,71 og Gardner-Holdt-visko-sitet D-E.204 g of hydroxypivalyl hydroxypivalate, 34.3 g of benzoic acid, 4.2 g of hydroquinone, 2.1 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction mixture is heated to 100 ° C for 5 hours and 40 minutes. 79.3 g of acrylic acid are then added dropwise over 20 minutes at 97 ° C to the reaction mixture. The reaction is continued at 96 ° C for an additional 4 1/2 3 hours. During the reaction, 120 cm of cyclohexane is added and 35.0 g of water is distilled off. The resulting monomer is obtained in a yield of 86.3% by weight after purification by washing. The product has neutral acid number, hydroxy number 31.71 and Gardner-Holdt viscosity D-E.
Eksempel 6 204 g hydroxypivalylhydroxypivalat, 96,9 g smørsyre, 3,8 g hydroquinon, 1,9 g svovlsyre og 50 g cyklohexan anbringes i en reaktionsbeholder og opvarmes til 94°C. Der tilsættes 79.3 g akrylsyre i løbet af 1/2 time. Omsætningen fortsættes i yderligere 3 timer ved 96°C. Under reaktionen tilsættes 70 cm^ cyklohexan, og 38,9 g vand afdestilleres. Det resulterende produkt opnås i et udbytte på 88,4 vægt% efter rensning ved vask. Produktet havde neutralt syretal, hydroxytal 10,3 og Gardner-Holdt-viskositet A-.Example 6 204 g of hydroxypivalyl hydroxypivalate, 96.9 g of butyric acid, 3.8 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 94 ° C. Add 79.3 g of acrylic acid over 1/2 hour. The reaction is continued for an additional 3 hours at 96 ° C. During the reaction, 70 cm 2 of cyclohexane is added and 38.9 g of water is distilled off. The resulting product is obtained in a yield of 88.4% by weight after purification by washing. The product had neutral acid number, hydroxytal number 10.3 and Gardner-Holdt viscosity A-.
Eksempel 7 204 g hydroxypivalylhydroxypivalat, 79,3 g 2-ætylhexan-syre, 4 g hydroquinon, 2 g svovlsyre og 50 g cyklohexan anbringes i en reaktionsbeholder og opvarmes til 99°C i 3 timer og 10 minutter. Derefter tilsættes 118,9 g akrylsyre i løbet af 30 minutter. Omsætningen fortsættes i 4 timer og 40 minutter. I lø- 3 bet af reaktionen tilsættes 168 cm cyklohexan og 2 g svovlsyre, og 38 g vand afdestilleres. Den resulterende monomer opnås i et udbytte på 88,5 vægt% efter rensning ved vask. Produktet har hydroxytal 32,31 og Gardner-Holdt-viskositet A-.Example 7 204 g of hydroxypivalyl hydroxypivalate, 79.3 g of 2-ethylhexanoic acid, 4 g of hydroquinone, 2 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 99 ° C for 3 hours and 10 minutes. Then 118.9 g of acrylic acid is added over 30 minutes. The reaction is continued for 4 hours and 40 minutes. In the course of the reaction, 168 cm of cyclohexane and 2 g of sulfuric acid are added and 38 g of water is distilled off. The resulting monomer is obtained in a yield of 88.5% by weight after purification by washing. The product has hydroxytal 32.31 and Gardner-Holdt viscosity A-.
Eksempel 8 15 U6067 204 g hydroxypivalylhydroxypivalat, 168,6 g 2-ætylhexan, 4,4 g hydroquinon, 2,2 g svovlsyre og 50 g cyklohexan anbringes i en reaktionsbeholder og opvarmes til 99°C i 20 minutter. Derpå tilsættes 79,3 g akrylsyre dråbevis i løbet af 1/2 time. Reaktionen fortsættes i 5 timer ved 98°C. I løbet af reaktionen til-sattes der 140 cm cyklohexan og afdestilleres 29,2 g vand. Den resulterende monomer fås i et udbytte på 71,9 vægt% efter rensning ved vask. Produktet har syretal 5,56, hydroxytal 53,84 og Gardner-Holdt-viskositet A-.Example 8 204 g of hydroxypivalyl hydroxypivalate, 168.6 g of 2-ethylhexane, 4.4 g of hydroquinone, 2.2 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 99 ° C for 20 minutes. Then, 79.3 g of acrylic acid are added dropwise over 1/2 hour. The reaction is continued for 5 hours at 98 ° C. During the reaction, 140 cm 2 of cyclohexane was added and 29.2 g of water was distilled off. The resulting monomer is obtained in a yield of 71.9 wt% after purification by washing. The product has an acid number of 5.56, hydroxytic number of 53.84 and Gardner-Holdt viscosity A-.
Følgende eksempler (9-12) er anvendelseseksempler.The following examples (9-12) are examples of applications.
Eksempel 9Example 9
Akryloxypivalylakryloxypivalat fremstillet ved metoden ifølge eksempel 1 hærdes på følgende måde:The acryloxypivalyl acryloxypivalate prepared by the method of Example 1 is cured as follows:
En stålplade overtrækkes med en blanding bestående af 100 vægtdele akryloxypivalylakryloxypivalat ifølge eksempel 1 (efter at hydroquinon er blevet fjernet) og 1 vægtdel kumen-hydroperoxyd. Blandingen opvarmes i nitrogenatmosfære ved 77°C i 30 minutter. Det resulterende hærdede produkt er en hård, skramme-plet-resistent film.A steel plate is coated with a mixture of 100 parts by weight of acryloxypivalyl acryloxy equivalent of Example 1 (after hydroquinone has been removed) and 1 part by weight of cumene hydroperoxide. The mixture is heated in a nitrogen atmosphere at 77 ° C for 30 minutes. The resulting cured product is a hard, scratch-resistant film.
Eksempel 10Example 10
De i eksemplerne 1, 2, 3, 4, 6, 7 og 8 fremstillede akrylmonomerer hærdes ved at blive udsat for ioniserende bestråling på følgende måde:The acrylic monomers prepared in Examples 1, 2, 3, 4, 6, 7 and 8 are cured by being subjected to ionizing radiation as follows:
Monomererne påføres på aluminiumplader og udsættes for elektronstråling ved en accelererende spænding på 400 kilovolt og en rørstrøm på 16 milliampére. Filmen modtager en total strålingsdosis på 4 megarad. De hærdede film har fortrinlig modstandsdygtighed mod skrammer, er meget hård og modstandsdygtig over for pletter forårsaget af blæk, thimerosal og sennep.The monomers are applied to aluminum plates and subjected to electron radiation at an accelerating voltage of 400 kilovolts and a tube current of 16 milliamps. The film receives a total radiation dose of 4 megarad. The cured films have excellent scratch resistance, are very tough and resistant to stains caused by ink, thimerosal and mustard.
Eksempel 11Example 11
En blanding af 75 vægtdele akryloxypivalylakryloxypivalat fremstillet som i eksempel 1 og 25 vægtdele 2-ætylhexylakrylat 146047 16 copolymeriseres ved at blandingen udsættes for elektronstråler ved en accelererende spænding på 400 kilovolt og en rørstrøm på 16 milliampére. Den totale strålingsdosis tilført blandingen er 4 megarad. Den resulterende copolymer er hård, er modstandsdygtig mod skrammer og plettes kun i meget ringe grad af blæk, thi-merosal og sennep.A mixture of 75 parts by weight of acryloxypivalyl acryloxypivalate prepared as in Examples 1 and 25 parts by weight of 2-ethylhexyl acrylate is copolymerized by exposing the mixture to electron beams at an accelerating voltage of 400 kilovolts and a tube current of 16 milliamps. The total radiation dose delivered to the mixture is 4 megarad. The resulting copolymer is hard, resistant to scratches and stained only to a very low degree by ink, thimerosal and mustard.
Eksempel 12Example 12
Produktet ifølge eksempel 4 polymeriseres på følgende måde:The product of Example 4 is polymerized as follows:
En stålplade overtrækkes med en blanding af 100 vægtdele af produktet ifølge eksempel 1 (efter af hydroquinon er fjernet) og 1 vægtdel kumenhydrogenperoxyd. Blandingen opvarmes i nitrogenatmosfære ved 77°C i 30 minutter. Den resulterende hærdede film var hård, modstandsdygtig mod skrammer, modstandsdygtig over for pletter og relativt bøjelig.A steel plate is coated with a mixture of 100 parts by weight of the product of Example 1 (after removal of hydroquinone) and 1 part by weight of cumene hydrogen peroxide. The mixture is heated in a nitrogen atmosphere at 77 ° C for 30 minutes. The resulting cured film was tough, scratch resistant, stain resistant and relatively flexible.
Claims (3)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82067269A | 1969-04-30 | 1969-04-30 | |
US82067269 | 1969-04-30 | ||
US82797469A | 1969-05-26 | 1969-05-26 | |
US82797469 | 1969-05-26 |
Publications (2)
Publication Number | Publication Date |
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DK146047B true DK146047B (en) | 1983-06-13 |
DK146047C DK146047C (en) | 1983-11-07 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DK213370A DK146047C (en) | 1969-04-30 | 1970-04-28 | POLYMERIZABLE MATERIALS FOR PREPARING COATS WITH GOOD SPOTTING, SCREAM AND SCRAP FACTOR, AND METHOD OF PRODUCING THEREOF |
Country Status (5)
Country | Link |
---|---|
DE (1) | DE2020419C3 (en) |
DK (1) | DK146047C (en) |
FR (1) | FR2056170A5 (en) |
GB (1) | GB1260269A (en) |
SE (2) | SE393371B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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BE793646A (en) * | 1972-01-03 | 1973-05-02 | Gaf Corp | STABLE SIZE COVER SLABS |
US5243069A (en) * | 1981-12-11 | 1993-09-07 | Rohm And Haas Company | Ester of Michael addition homopolymers of acrylic acid |
DE3204504A1 (en) * | 1982-02-10 | 1983-08-18 | Henkel KGaA, 4000 Düsseldorf | NEW SERIOUS MONO AND / OR BIS (METH) ACRYLATES AND THEIR USE |
US4775732A (en) * | 1988-01-11 | 1988-10-04 | Allied-Signal Inc. | Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3320336A (en) * | 1963-11-14 | 1967-05-16 | Eastman Kodak Co | Unsaturated polyesters having branched structures |
GB1135647A (en) * | 1965-06-29 | 1968-12-04 | Grace W R & Co | New esters |
US3470079A (en) * | 1966-05-18 | 1969-09-30 | Ppg Industries Inc | Highly radiation-sensitive telomerized polyamides |
-
1970
- 1970-04-27 DE DE19702020419 patent/DE2020419C3/en not_active Expired
- 1970-04-28 SE SE589770A patent/SE393371B/en unknown
- 1970-04-28 SE SE7314202A patent/SE396757B/en unknown
- 1970-04-28 DK DK213370A patent/DK146047C/en not_active IP Right Cessation
- 1970-04-29 GB GB2057070A patent/GB1260269A/en not_active Expired
- 1970-04-29 FR FR7015681A patent/FR2056170A5/fr not_active Expired
Also Published As
Publication number | Publication date |
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GB1260269A (en) | 1972-01-12 |
DK146047C (en) | 1983-11-07 |
DE2020419A1 (en) | 1971-01-14 |
FR2056170A5 (en) | 1971-05-14 |
DE2020419B2 (en) | 1977-06-30 |
SE396757B (en) | 1977-10-03 |
SE393371B (en) | 1977-05-09 |
DE2020419C3 (en) | 1982-07-22 |
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