DD276691A1 - METHOD FOR PRODUCING (METH) ACRYLATED MINERATED LIQUID POLYMERS - Google Patents

Abstract

Process for the preparation of (meth) acrylate-terminated liquid prepolymers of the general formula CH2CCOO R OOCCCH2 RRaus hydroxyl-terminated Telechelen by reaction with esters or anhydrides of methacrylic or acrylic acid or by direct reaction with methacrylic or acrylic acid in the presence of condensing agents, such as dicyclohexylcarbodiimide, wherein R is homo or copolymer of 1,3-dienes and / or vinyl monomers, which is obtained by stoichiometric reaction of the monomer (s) with dilithiumditertiary diamines and subsequently converted into the a, v-diol form with oxiranes.

Description

After distilling off the ether and drying, the (moth) acrylntterminierte Flüsoigprepolymere remains, which is now available as a comonomer with reactive (meth) acrylate end groups for the corresponding polymerization reactions.

Blends of non-functionalized or hydroxyl-terminated hydrophobic liquid prepolymers to the usual and relatively polar acrylate or methacrylate monomer approaches prove to be problematic due to the incompatibility and the associated phase separation. After polymerization of the acrylates, the liquid prepolymer often diffuses out of the polymer matrix, limiting its applicability to flexibilization of polyacrylate (methacrylate) gauzes. To avoid these disadvantages, therefore, the direct inclusion of appropriately functionalized, ie (meth) acrylate-terminated, telechelic α-bonds in polymers is necessary. The (meth) acrylate-terminated liquid prepolymers according to the invention have a narrow molecular weight distribution which is attributable to the production process of the α , ω-diols and proves to be advantageous for the flow behavior and the viscosity of the prepolymers.

example 1

Into a 250 ml sulfonation flask with a transfer tube, internal thermometer, distillation head and stirrer, 10 g (7.13 mmol) of hydroxyl-terminated butadiene prepolymer (prepared according to DD 241603A1), 30 ml (318.13 mmol) of methyl methacrylate and 0.1 g of hydroquinone are introduced and argon is introduced. Then 0.2 g of sodium methoxide are added and the mixture? Are heated with stirring to 90 ° C. After 2 and 4 hours, a further 0.1 g of sodium methoxide is added.

After cooling, the reaction mixture is filtered off with suction, the salt residue washed twice with methyl methacrylate and distilled off from the combined filtrates methyl methacrylate. Then the residue is taken up in 40 ml of ether, washed with water, 4% sodium hydroxide solution and twice more with water. Thereafter, the ethereal solution is dried over Na ₂ SOj dried over kieselgol and acid Airminiumoxid and then distilled off the ether. What remains is a methacrylate-terminated liquid prepolymer, which exhibits the typical absorption of the ester grouping in the IR spectrum at ν = 1 724 cm 'and no longer absorbs any absorption of the hydroxyl groups in the region 3200-3600 cm'.

Example 2

30g (22,19mmol) hydroxyl-terminated butadiene prepolymer are dissolved in 150m! dissolved in dry toluene. 5.354 g (42.77 mmol) of acrylic acid anhydride are added dropwise with stirring. Stirring is continued for 4 h and the toluene is distilled off in a water-jet vacuum. The product is dried for 6 hours at 5 × under oil pump vacuum and stabilized with 100 ppm hydroquinone. The IR spectrum shows the ester band at 1735 cm 'and an OH band in the Boreich 3200-3600 cm'.

Example 3

10.2 g (7.54 mmol) of butadiene prepolymer and 2.1 g (29.14 mmol) of acrylic acid are dissolved in 50 ml of methylene chloride and cooled to 0-5 ° C. While stirring and cooling, 3.0 g (14.54 mmol) of dicyclohexylcarbodiimide dissolved in 20 ml of methylene chloride are added dropwise. The mixture is stirred for ⁴ h at 0-5 ¹ C and heated with stirring to room temperature. It is then filtered off with suction and the methylene chloride distilled off in a water-jet vacuum. The product is dried in an oil pump vacuum for 6 hours and stabilized with 100 ppm hydroquinone.

The IR spectrum shows the absorption of the ester group at 1735 cm ', that of the OH groups at 3 200-3 600 cm' is no longer observed.

Claims (1)

Process for the preparation of (meth / acrylate-terminated liquid prepolymers, characterized in that acrylate-terminated liquid prepolymers are prepared by reacting hydroxyl-terminated telechelates with esters or anhydrides of methacrylic or acrylic acid or directly with methacrylic or acrylic acid in the presence of condensing agents, such as dicyclohexylcarbodiimide (meth) . wherein R contains a carbon chain represented by anionic homopolymerization or copolymerization of 1,3-dienes and vinyl monomers obtained by stoichiometric reaction of the monomer (s) with dilithium di-tertiary diamines followed by reaction of an epoxide such as ethylene oxide, propylene oxide or styrene oxide into the c, ω-diol form is converted and R 'is CH ₃ or H. Field of application of the invention The invention relates to a process for the preparation of (meth) acrylate-terminated liquid prepolymers in the MW range of 500-50 OOg / mol. The (acrylate-terminated) liquid prepolymers of the present invention are free-radical, including photocyclic, polymerizations and are useful as hydrophobic and floxibilizing comonomers, and the like. for (meth) acrylate or SH / en polymerization, for the production of adhesives for precision instrument construction, as well as for use in laminates, casting resins, composites u.v.a.m. suitable. Characteristic of the known technical solutions For some time, various α, ω-functionalized prepolymers of 1,3-dienes and / or vinylmonomorone have been known. Most of these products have been prepared by free-radical polymerization (DE-OS 1150205, DE-OS 1259575, US 3235589) and have the known disadvantages of a broad Molekulargewichεverteilung and the occurrence of mono- and higher functional species It is known that (meth) acrylate-terminated styrenic prepolymers were obtained by reacting styrenic prepolymers with methacryloyl chloride (Makromol Chem, Rapid Commun., 3,198,221,499), which, however, do not affect the present invention. Object of the invention The aim of the invention is to avoid the disadvantages of known processes and prepared in an anionic manner with Dilithiumditertiärdiamininitiatoren homopolymers and copolymers of 1,3-dienes and / or vinyl monomers, which carry α, ω-position hydroxyl groups, in a technically easy to implement Modify the procedure so that bifunctional (meth) acrylate-terminated telechelics can be prepared. Explanation of the essence of the invention The object of the invention is achieved by converting special hydroxyl-terminated telechels 1 into (meth) acrylate terminated liquid prepolymer 2 by transesterification with acrylic or methacrylic acid esters: ii ,, where R is a CC-Ketto onthölt represented by anionischo homo-odor copolymerization of 1,3-dione and Vinylmonomoron, dio by stöchiomotrischo Roaktion dor or dos Monomeron with Dilithiumditortiärdiamincn and iinschlioßnnd with oinnm Epox'd, wio ethylene oxide, propylene oxide odor styrene oxide o in the α, ω-diol form is wurdo and R 'is CH] or H. Dio Hoistollung (moth) acrylatto'miniortor Liquid Propolymore 2 also succeeds boi prewonding of Mothacryl- odor Acrylsäuroonhydrid (R "CH ₂ CR'-CO) odor by using Mothacryl- odor Acryl.iäuro (R" --- H) when Kondonsntionsmittol , wio boispiolswoiso dicyclohoxylcarbodiirnid, angowondot wordon. Dio hiorbei m nrfindungsgomäßon Propolymnron nocli onthaltonun Rosto of acrylic odor methacrylic acid wordon distillotively removed in vacuo or abgotronnt in the case of the, N.N'-Dicyclohoxylharnstoffos by oino steam distillation. (Moth) acrylaltorminiorto Flüssigpropolymoro wordon boispiolswoiso wio follows: The hydroxyltorminiorto Flüssigptopolymoro is together with acrylic or methacrylic acid methyl ester, in Gogonwart of hydroquinone, and after addition of Natriummothanolat siobon Stundon under Ar protective gas utif 90 "C warmed to dom Abkühlon is evaporated , Methanol and MMA abdostilliort, dus liquid propolis in Ethor aufgonommon and gowaschon.