DD208468A3 - METHOD OF MANUFACTURING VOLATILE POLYESTERETHER - Google Patents

Abstract

The aim of the invention is to make the very small volume contraction of spiroorthoesters for the production of low-stress polyester ethers while avoiding the defects in the previously known polymerizations of Spiroothoestern technically usable. The object of specifying a process with which it is possible to polymerize easy-to-use, stable and easily prepared spiroorthoesters to low-stress polyester ethers is achieved by dissolving 2-isobutyloxymethyl-1,4,6-trioxa prepared from gamma-butyrolactone and isobutyl glycidyl ether. spiro- (4,4) -nonane either alone or with up to 30 mole% of 2,2-bis (1,4,6-trioxaspiro (4,4) -nonan-2-methyloxphenyl) -propane in the presence of Et deep 3 O high plus SbCI high minus 6 is polymerized. The polyester ethers prepared according to the invention can be used as optically clear polymer molding materials, precision adhesives or structural adhesives in the optical industry.

Description

~; / _ y ϋ U ν »

low voltage P

Verfahreα. for the production of low-stress polyester ethers

Field of application of the invention ;

The invention relates to a process for the preparation of low-tension polyester ethers _? which have a broad technical utility profile. They can find application in the optical industry as optically clear polyser mold materials , coating materials, precision adhesives or as structural adhesives.

Characteristic of the known technical solutions :

For the production of polyterthreads, are procedures known _? which are based on the polj / iserisaticn of spiroorthoesters. Of shelf section, however, it is ₃ that 'he Spiroorthoest used are crystalline compounds and can therefore be worked only above their melting point "* This results in the further Htachteii that the low Lagerstabiiität for triggering depolymerization necessarily hinauzumisehende initiator under these temperature conditions of the Monomer mixture and thus too short processing time s caused *

It is also known a method in which trioxane is used as Comonorrieres and solvent for spiroorthoester use. (J? -? At «65-3708, see also CA. S3j 11732 h (1965))» The defect, however, is that

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2 - -LL - * "? W w -w ί /

that with the BF-j-EtpO used as polymerization catalyst only a polymer yield τo α 40% is achieved. Incidentally, two spiroorthoesters of the following formula are in the literature

E ¹ ρ R Jfci α. ρέγ ρ η ^ν -ρ ο - b H

5 C

f Y ²

CH ₂ -CH ₂ . ,

Dia., 622, 183, (1959); J * Polym, Se, "Polym" Lett, 1j3, No. 1, 25, - (19SO)) are known to be liquid under standard conditions. However, the spiroorthoester a has the defect that it is extremely sensitive to moisture, which is known to significantly interfere with the cationic ring-opening polymarization and produce only low-molecular-weight polymers. Although the 3-ring spiro-orthoester b is easy to handle, the cationic ring-opening polymerization presents problems in that it causes problems the reactivity of the chloromethyl group leads to chain termination reactions and transesterifications, γ / ο are formed by only yellow-colored oligomers. Also known is another liquid spiroorthoester which polymerizes thermally-radically and cationically

A ρ

is bar and in which in the above formula R '/ R ~ by a = CH _p group is represented (J? -Pat, 1215S4-79: DE-OS 3035431) * Ia this case, it is τοπ. Significant disadvantage j that the mono-nerenumsatz in the polymerization is only very low , so that use of the resulting polyester ether comes only after a cleaning by falling into consideration.

All known Spirοorthoester have the common feature that their polymerization with a very low. Volume nk ο nt r actlon τ running (total s chr e p t e s ag e s from 0.5 to max 2%). Caused by the above-described and from the iohys! Kauscheη and chemical properties as well as from the reaction-related. conditions

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Rrm j * WV ^ • i; = / '.4 /

resulting deficiency _? There is a significant disadvantage of the prior art is that the so significant effect of low volume polymerization of the spiroorthoester technically could not be harnessed for the production of low-voltage polyester esters and their application as polymer molding materials or adhesives.

Object of the invention:

The aim of the present invention is to overcome the deficiency and Fachteiie of the prior art, In particular, the very low Yolumenkontraktion in the polymerization of Spiroorthoester for the preparation of low-voltage Poiyesterethern be made technically usable, at the same time a large storage stability of the Monomerenansatzes up to several weeks and a technologically acceptable pot life up to 3 days should be guaranteed. In addition, the moisture sensitivity of Spiroorthoester should be eliminated and a complete Monomersumsats be achieved at the same time high molecular weights. "According to the objective, the polyester ethers to be produced should be completely colorless and OOtisch clear.

-O

Loan the essence of the invention :

In order to realize the objective, it is the task of the present invention. Invention to provide a method by which it is possible to easily to handle, stable and easy to produce Spiroorthoester to low-voltage Poiyester ethern polymerize, According to the invention, the .Aufgabe by a method.

dissolved to prepare 'of low-stress Poiyesterethern from Spiroorthoestern, which is characterized in that y-butyrolactone and Isobutylglycidether in the molar ratio 1: 1 to 2:? 1 in tetrachloroethane ^ 5 ^ s kohlen.stoff as solvent at 30 ^J C in the course of 5 hours in the presence of 3F-, · Et ^ O as catalyst to the spiroorthoester 2-isobutyloxymeth, yl-1 * 4.6.-trioxa-spiro- | ^ U 4j -nonane are reacted, Bas obtained in this way. 2-isobutyloxymethyl-1,4,6-trioxa-spiro-i4.4) -nonane will continue to be used.

-A-

U O ο \ /

according to the invention, either alone or with a proportion of up to 30 mol% therein, dissolved, according to WP C 08 G / 234 316-5 producible 2 _? 2-Bis- (i.4.6-trioxaspiro-I 4 * · 4; -nonan-2-methyloxyphenyl) -propane in counter-V / type of St ^ O ⁺ SoClT in an amount of 1 to 3 .Gew "-% based on the j Spiroorthoestermenge, at 80 to 100 ⁰ C in the 'erlaufe polymerized' τοπ 6 to 8 hours. Experienced ^{v in} this invention, a storage stability of the monomer approach of several. Weeks.

, achieved _} without crystal precipitation or other turbidity occur. The starting monomers and their mixtures are not sensitive to moisture The pot life of the polymerization batch is more than 72 hours, the gel time at 10O ⁰ C still about 1 hour .. The polymerization, runs under a complete Monomerenumsatζ and leads to high. Molmasseη the polyester ester. which are also completely colorless and optically clear. The total volume ion traction during gel formation and terning is 1 to 1, S, depending on the mixing ratios of the monomers. Polyester ethers prepared in this way are low in stress and flexible in a broad temperature range Resistant to micro-cracking and resistant to shock-like. Temperaturvreohsslj for example in the 3e_ range from -40 ⁰ C to + SO ⁰ C, '' glued with the aid of the method according to the invention glass parts ₅ such as lenses ^ plane plates and similar optical components are mechanically inseparable at room temperature. If necessary, they can be separated by heating to 15O ⁰ C for a few minutes or by treatment with boiling chloroform *

Execution s in so ie ₁ :.

The invention will be explained in more detail with reference to the following Ausführungsoeisp-iele.

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403 3 1 'Ζ

example 1

172 g (2onol); -p-butyrolactone were dissolved in 600 ml of tetrachloro-carbonyl compound and 6 parts of 3F _n ⁴ St ₀ O. With stirring, 260 g (2 mol) of isobutyl glycidyl ether are added dropwise at 30 ° C. for 2 hours, then according to one still. React for 3 hours and mixed with 300 al 10biger I ¹ IaOH ₃ destroy the catalyst au. The organic phase is separated, dried with 2LC0-, and distilled »First, the solvent is removed; then the residue is fractionated in the vacuum. This gives 250 g of the spiroorthoester 2-Isobutyloxyui3thyl-1 "4-, 6-trioxa-spiro ' _U 4" 4J -nonane as a water-clear liquid

Bp ₄ : 72 to 74 ° C / 33 mPa

Ή _Ώ ² ° = 1.4438; ^ ²⁰ = 1.0383 g ° cm ^-3 .J ₁ Hp ₀ O ₄ calc .: C 61.09 $ Ξ 9.32% 216.24) Found: C, 60.93 # H 9

The same results are also obtained using 130 g (1 mmol) of isobutyl glycidyl ether.

0.1 g of Et ^ Q ⁺ SbClT at 40 to 5O ⁰ C nonane brought into solution with Bühren - 10 g of 2-Isobut3 / loxymethyi-1 .4.6-tr Ioxa-spiro [4 * 4]. This ready-to-use Polymerisationsansata is usable in a sealed vessel for 3 days and polymerized at 1QO ⁰ C in the ^v orrlaufe of 8 hours in a sealed FormgefäS or as an adhesive layer between optical components to a low-voltage colorless, optically clear polyester ether of the general formula ·

C 6

CH ₂

O ntj _ ruf r ^r J ^]

where η is -10 to 15 and the total volume shrinkage is 1.6 ^. The Tg point of the polyester ether

^w o? ü - 3

is at -35 C ₃ its density is ~ ~ - 1,055 g * approx

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    Example 2

A solution τοπ 20.506 g (0 ^ 04 mol) of 2 * 2-bis (i, 4.6-trioxa-spiro [4.4J-nonane-2-inetjayloxyp] aenyl) -propane prepared according to WP C 08 G / 234 816-5 - in 25.95 g (0j12 mol) 2 ~ isobutyloxymeiiyl-1, 4. 6-trioxa spiro_4,4- | nonane - prepared as indicated in Example 1 - is added with Oj75 g Et-, 0 ⁺ SbCl7. The initiator is reacted at 40 to 5O ⁰ C with stirring into solution and the yellow-colored polymerization · the location at Raumteraperatur in sealed vessels several 'vsrv / ending _capable} subsequently remains at 10O ⁰ C in Terlaufe of β hours in a sealed 5Oringefäi3 or as an adhesive layer between optical components' polymerized. The resulting polyester ether is colorless and

ρ 0 -1

visually clear -, 'The density is .P ~ = 1,11.7 g' ca, the total volume swirl during the polymerization process is ca, i _} Q% *

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Claims (1)

- ^ rf j- Π- du ό '- * s to T) u eil « Process for the preparation of spann.un.gsordnet PoIyesterethern from Spiroorthoestern, characterized in that ν- »-But, yr o la et on and Isobutylglycidather im J itlOi »o« Ild ± l <iiia 1 · ί U - o ^. · 1 J. HiOi (iC.uu ^ .wi. ". Buieiiö.uuii Cj. O Solvent at 30 "C over 5 hours in the presence of τοπ BF -," StpO as catalyst ranges et zt be and the thus obtained 2-Isobutyloxymsthyl-i * 4.δ-trioxa-spiro - [] 4,4J-nonane either alone or with up to 30 mol $ au dissolved therein 2, 2-bis (I 4, δ-tricxa-spiro- r4,4l-nona:. n-2-2istliylo: Q ^T phen.7l) propane in the presence of 3WO ^ SoClJ in an amount το η 1% by weight to 3 G-3w-%, based on the /-1 Spiroorthoestermenge _{} be} polymerized at SO to 100 C in the course τοη 6 to 8 hours. 3981