DE1595479A1 - Process for the production of cast plates from methacrylic acid methyl ester - Google Patents

Description

GOLD « XSND SILVER ^ SCHEIDEANSTALT FORMERLY ROESSLBR Frankfurt ara MaIn ₀ Weis» women st ras a β 9

Vosrfahron E «r manufacture of cast plates from

Methacrylic acid methyl ester

Ea iat known, Polymefchacrylaäuremethyletern or Poly "uiovisateiij die ± ra woaon * borrowed on from" Imothacrylaauremethyl "^ aster have been produced (so-called acrylic glass) _t by hardening eixio greater hardness and scratch resistance as well as oinoii higher resistance to heat and heat. oit au verloiiien »On the glacial side, this cross-linking essentially prevents the sensitivity to solvents and thus the susceptibility to savings

By networking ausserdom is eri-calibrates that the well "modeling: the Eunstatoffes ausseiHäuslich thermoelastically _P thus without thermoplastic proportion ₉ ai'folgto This is Oino gloichmässigare thickness distribution and dazalt a larger Foatigkeit in extended form body reaches and Z ₀ B ₀ in opaque material an improved edge illumination caused o With a unehmondena Vernetaerhalt the products are increased eprödor and the Schubraodul in the thermo-relaatiochen area; whereby the force required for hot forming increases or the hot formability decreases,

Ee iet known; ejx keeping the thermoformability of crosslinked products by using two different types of crosslinking agents (German patent Ö7k 37t) _o In this process, crosslinking agents with groups that crosslink in the manner of a valonz; such as diacrylates, Divlnyiverbindungen USWo ₀ blndungen with Ver "having nobenvalenzartig crosslinking groups ^

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such as Acryianuid ;, Acrylic acid usvr- _; . © ing «ßet. ^ *. In doing so, batonta will obtain the »when used alone by the xuerat named Vernetssergruppe products that are neither deformable nor machinable <These products © are brittle ^

It is also known that there is a high degree of polymerisation hunts tfärniei'ormbeatständigkeii through »! iaciipolymorisiation of a-Be Methacrylic acid methyl ester with an ethylitol ion compound (German Auslogesehriften 1 HO ^ - 7 ^ 0 and

In the previously known processes, however, very long polymerisation times have to be taken into account. The ethylidene compounds a _o B are only preparatively difficult to use ₃ while the compounds mentioned with groups that cross-link like valena have a strong adhesion to the glass when glass forums are used show what causes separation difficulties ο

May finally it is also known ₃ that the molecular weights of polymers by the addition of so-called regulators decrease in the polymerization "For example, you can this hydrocarbons, particularly those containing tertiary hydrogen atoms have _p chlorinated hydrocarbons, alcohols, and mercaptans verwendenο The addition of mercaptans to jeodch O ₀ D ^, based on the monomer, do not exceed _p because larger amounts do not produce any advantages, and when using significantly higher amounts, even products are obtained whose properties are worse than those of those produced without a regulator (British Patent 736 620) _o

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He. vmicde now found t, the «tian cast plates by Sttb? iftan.; ^ c.rs ₍ nKe. ^T risatiQini vom. äki v / esentliehen aua monomeric! methacrylic acid crnetlrylpsteK * and given exit all polymethacrylic acidic hyiester consisting of mixtures rait the help of Catalysts which form free radicals or Hodox catalysts, if necessary at elevated temperatures, can be produced in (5% iart of additives which change the properties of the finished plates) if at the same time from about O ₅ I to about 10 mole percent are present fbeascif ^ n on the monomer) at least one a fore-notation and et ν / α O ₅ Ot until about "! mol percent of at least one ler polymerized."

Additions ο which change the properties of the finished panels _p are intended to protrude ± vx framework dor present invention per se known Vernetaer and Kegler ^

By orfindvmgsgemässe process products are obtained "having the advantages dor crosslinked polymers and is superior in its overall Provision in the thermal deformation of the non-=-crosslinked products are" advantageous is may further _D that is shorter in this ancestors substantially polymerization times *. Even with short polymerisation times, the process products are of perfect quality »

All compounds known for this purpose can be used as pre-wetting agents (CοEcSchildknecht “Vinyl and Related Polymers”, J Wiley N.Yo ΐ952, So 208 and 209? Houben Veyl “Methods of Organic Chemistry ·% G.Thieme Verlag ₉ Stuttgart 1 ° 6i _e Volume XIV / i, .. So 32 - 33 s H λ Lücke "The Technology of Organic Glass * ¹ , Kunststoff" Rundschau, July 1962, Issue 7, So 331 B _B b) .Aliphatic "

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Hydrocarbons rait sew © A and more double bonds in the molecule so compounds of the * type dos butadiene j are here aixsgeechXeseen ZB-come strongly crosslinking monomers, such as di- (moth) acrylates diacylates or divinyl compounds ρ aB Glykoldiraethacrylat and -acrylate di «or» Triethyleneglycol diinothaerylate and acrylates Glycerintriraethacrylat, MethyXenblaacrylanrid und -methacrylamides Triacryloylperhydrotrias'JLtt, Divinylbonsol, Methacryleäure vinyleater ,, Metiiacrylsäu / r © anhydrid _s itiüseic, Etiotloethö Ä ‰ äth, aliatloethacrylic acid methacrylate! or weakly crosslinking monomers ρ such as Di- _P Tri, Tatra etc ^ Allylvorbindungenj, for example diallyl phthalate "diethylene glycol bis ^ aJLlylcarbonat, triallyl cyanurate _s tetraallyloxyethane, triallyl phosphate _s diallyl fumarate, or mixtures of different crosslinkers are used" when using the three Ali.yl compounds and more aiiylgxiippeii aufwal zen "äi.E triallyl cyanurate"

Triallylieocyanuratj Tetraallyloxyätbcta etc., _P can be found in plates "which can be further thermally deformed into molded bodies with an increased refractory temperature."

The crosslinkers are used in such proportions _p that are critical degree of crosslinking (Houben Veyl 196T _p tape XIV / f _p "Macromolecular Materials I" ₀ Sc 305) is exceeded, and products which are insoluble in the usual solvents "The upper limit of the cross-linking agent is given by the course of the shear modulus of the products as a function of the temperature. At temperatures below the decomposition point, this should reach the limit of malleability, ie drop to at least 7 χ 10 'dyn / cra (soGnSchreyer,

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"3d * 55» H9u5 .. Booklet 5 » S- 3 * 2), bew, the ira limit of 100 kp / em *" (9 * 8 χ H (T dyn / era ") specified for DIN 772 * for thermosets fall below “For example, it is recommended” for strongly crosslinking compounds about OgI to about ΐ _Ρ 0 percent, for moderately strong crosslinking compounds about 0 “t to about 5 mol percent and for weakly offensive compounds about 0 _s 5 to about 10 Use pick-up percentage.

In the context of the present invention, all known controllers? zJn the classes mentioned in Houben ¥ © yl ΐ96ΐ ₀ Volume Xiv / t ₉ ^ Macromolecular substances X% S * 66 ffΌ ρ are used «But aliphatic mercapto compounds are preferably used. Alkyl mercaptans and the esters of mercaptoacetic acid. The precautionary amounts for the regulator are between about O ₁₁ OS and O ₀ 5

The monomeric methyl methacrylate serving as the starting material, which must be present as an essential component in the starting mixture, may contain other polymerizable monomers ₈ such as higher esters of acrylic or methacrylic acid, acrylonitrile, styrene, vinyl toluene, etc., mixed in

It is also possible to start from prepolymers which are regulated, if appropriate, and which are produced in a manner known per se by partial polymerization can be obtained if in these prepolymers from the manufacturing point of view, regulators are available, so muse the addition of these substances can be reduced accordingly during further polymerization »

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But it is also possible from LSsungou dea polymers in the

Aspirate monomers. Here 3: .ann the polymer auofc

Vernotzer Such nongenes contain _s tiaes of the critical ©
Degree of plastering not exceeded

In addition, the Ausgangsmomowere can brsi- / · dae monomer mixture all customary in the production of acrylic glasses additives such as plasticizers ρ _s Pi & mante _g dyes »Stabiliaatoren w etc""enthaltenο

The polymerization takes place in an orphan known per se
Temperatures from about room temperature to about iho ^u C carried out »It can be carried out in the presence of a odor several radical-forming catalysts for this purpose, for example, azo compounds such as assodiisobutyric acid dinitrile, and preferably organic peroxides ,, a .-, Βο hydro», alkyl, acyl, alkylacyl peroxides "In question" The simultaneous use of two or more different catalysts with different activities is often advantageous "

For carrying out the inventive method, so-called redox catalysts can ο be used These bestohen of at least one oxidizing and a reducing compound "> In particular, such systems are in question _(which is an organic peroxide compound on the one hand and a Arain, in particular a tertiary amine, on the other hand or contain organic sulfur compounds. In addition, further accelerators known per se can also be used ο

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DAo catalysts are used in amounts known per se

Bio manufacturing dor erfindungsgemUaaen Flatten can according κει "I j aucii known ancestors of the continuous bulk polymerization, it can be carried out advantageously * ₀ B in FLAC hkaminern! Z _c in particular of glass or metal, or _p sn-ri see films or on). ' olnom tape or by centrifugal casting ..

To 100 parts by weight of unatabilized methyl methacrylate O ₀ 2 ^w "ethylene glycol diraethacrylate and 0 _p 1""glycol dimercaptoacetate

₀ % part by weight of diisopropyl peroxydicarbonate and 0.1 part by weight of a 25% solution of diacetyl peroxide in diethyl phthalate are added for hardening.

The Anaats is evacuated at ^ 3 ° C with stirring for about 5 minutes and then _{poured into a polymerization cell p} consisting of 2 panes of glass (50 χ 50 cm) ₉ which is sealed with a 5 mm thick elastic piping ₉ and at + 60 ° C hardened in a water bath. The hardening time is 14 minutes. Leashing is done for 1 hour at 105 ° C in the circulation drying cabinet a * «Pie finished plastic is free of defects ο

■ '- ■ iifung duf Lösungemittolbeetändigkeit a Z χ h cm jx-OAEE r> be at room temperature in a mixture of acetone and methanol (l, i) "added to k sseigt hours there was no visible change?.

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To test the plates Temperaturbeständigkeit- represents a 4 cm χ to grosso P _r obe heated in a through bore in a freely suspended Umluftt ro Elco by rank ΐ hour at + i80 C ^ü "After this time shows no visible change

In the case of hot deformation - blowing a dome «becomes a good formation achieved,

For comparison, no crosslinking is added to the approach, only 0.1 part by weight of glycol dimercaptoacetate »

The hardening time in the water bath is 122 minutes

When testing for Lb'sungsmlttelbeetändigkeit the sample is dissolved at the surface k hours and weiseundurchsichtige In considering the heat resistance formed during the heating on ΐ80 · C enlarge the many bubbles "

Is the approach controller not only _e O ₉ 2 wt "parts by Äthylenglykoldiinethacrylat added, the hardening time in water bath is 99 minutes,"

The finished plate asked at all lateral edge zones of up to about 5 cm wide overflächliche unevenness and detachment ₀

During hot deformation - bubbles «in» the dome - no · good shape.

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Example. 2 s

Il ill, ί LI I ■ _ lfcill II ' mm

Aue wnBtabiltsies-tem methyl methacrylate is in the presence; from Oo wt Ii> parts by Glykoldiraeroaptoaeetat a syrup prepared (measured at + 20® C) having a viscosity of 2000 ep AsodJllsobu1ttersäurediiiife;. 'll is used as a catalyst Dor polymer content Amount * 26.5 i> * i> r ° $ .- »The value of the polymer in the syrup is O ₀ 52.

0 ₅ part by weight of diisopropyl peroxydicarbonate and ₀ 1 part by weight of diacetyl peroxide solution (25 parts in dimethyl phthalate) and ₀ 2 parts by weight of glycol dimethacrylate are added to the syrup.

D-Se hardness time in a water bath at + 60 ° C is k0 minutes _o The plate press is 1120 χ 200 cm.

The finished plate is free of defects *

In a 1 stundigen heating to 18O * * C, no visible changes * aeigen When tested for solvent resistance geciäss Example 1 also shows by h hours no visible Veränderungο

During hot forming on a deep-drawing machine with a Negative form with dimensions 180 280 80 mm «their side walls Have a ripple structure, good deformability is shown with a good mapping of the contours with uniform Wall thicknesses at the outermost corners,

The flexural strength of the finished plate, measured on Dynstat samples of k mm plate tens tärlco, is ΐ3 ^ 5 kg / cm and the Schlagbiegefeetlgkeit 10 _c 3 cmlcg / cm η

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Proceed as described in Example 2 *. However, instead of O ₉ I parts by weight of Glykoldiraercaptoaeetat, O ₉ IO weight of TeAIo n-Qc & y! Mercaptan are used *

The hard time in the water bath is 53 minutes <-

The finished plate is f © free here "In the one-hour Sr ψ hits young age ·} * 180 ⁰ C, aeigen no visible changes.

In the case of hot deformation, the deformability is equally good ability and even wall thickness distribution as in example 2

For comparison, the polymerization is carried out without ethylene glycol diniethacrylat performed.

The hardness tent in a water bath at -s-60 ⁰ C contributes 5k minutes *

The finished plate is flawless. When heated to + 180 ° C for 1 hour, many larger bubbles appear ο

example ks

100 parts by weight of mono inerer methacrylic acid methyl ester are catalyzed with 0.1 parts by weight of diieopropyl peroxydlcarbonate and 0.05 parts by weight of cyolohexanone peroxide and 0.2 part by weight of ethylene glycol dimethacrylate and 0 part by weight of octyl mercaptan are added »The mixture is in polymerized in the manner described in a mold made of glass plates in a water bath at about 60 ° C on a plate of k now thickness «The plate is solid after 2 1/2 hours and has a perfect surface ο The plate was 2 hours at 100 to 110 * C.

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DAo plate is made from the methanol-acetone mixture (i? ΐ) not attacked even after a long stohon <■ Doim Tiefsielien in a form of 80 ram height results in one (?: ute illustration of the edges. The minimum canton thickness is G ο 5

T-nm Yorfrleich becomes in the absence © Anea Mercaptans gearba & fcafc, the plates are firm after t 1/2 hours. The l-lines obtained, however, show a strong unrest in the randaones oine start c ⁰ ^^ * " ⁰ * ⁰ surface. They were not attacked by the above-mentioned methanol-acetone mixture Deformation possible The shape is shown only very inadequately '.

If you leave the front path in another cattle, the plate is also feet after ΐ ϊ / Ζ hourso However, it is strongly attacked by the solvent and is loosened after standing for a long time _o When deep-drawing does the edges appear well? the corners are, however, sucked to about Oj25 order.

Example 5s

The procedure is as described in example k , but 0.5 parts of ethylene glycol dimethacrylate and, 2 'c, -tiii octylmcaptan are used. The plate is solid after 1.5 hours and shows a perfect surface ^ Mp ^ c rl εΛ ^T st can also be set well deeply

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It is, as the procedure in the example k beeehriebon _c, but are GEWC 2 parts Allylniethacrylat and 0.1 wt «~ part octylmercaptan used ο The plate is feet by 2 1/2 hours, and also shows a satisfactory surface * It is against the above Said solvent geiaiBCh resistant and easy to deep-draw

Example 7 »

The procedure is as described in Example h , but 5 parts by weight of diallyl phthalate and 0.1 part by weight of octyl mercaptan are added. The plate is solid after 2 t / 2 hours and is of perfect quality, it is resistant to the soldering agent mixture and has good deep-drawability.

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Claims (1)

Pat Q ₁₁ η ta η a ρ r Ü che t Process for the production of cast plates by bulk polymerization of essentially monomeric! Methacrylic acid methyl ester and optionally polyethacrylic acid methyl ester mixtures with the aid of radical-forming catalysts or redox catalysts, optionally at elevated temperatures in the presence of additives changing the properties of the finished panels, characterized in that, in the simultaneous presence of about O ₉ ϊ to about 10 mol percent (based on the monomer) at least one crosslinker and about 0.01 to about 1 mol percent of at least one regulator polymerized « Process according to claim 1 _B, characterized in that "an aliphatic ^ mercapto compound is used as regulator" Process according to claims 1 or 2, characterized in that one uses a crosslinker _s of the three or more allyl groups in the molecule aufweisto 9> 2 <, 19th
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