DE2307088A1 - PROCESS FOR THE PRODUCTION OF POLYCONDENSATION PRODUCTS CONTAINING ESTER GROUPS WITH IMPROVED PROPERTIES - Google Patents

Description

WETCHHOLB ALBERT C f E *? -F

Patent registration

Process for the production of · containing ester groups Polycondensation products with improved properties

The invention "relates to the production of esters ■ containing polycondensation products, e.g. of unsaturated Polyester resins and alkyd resins, in repair of catalysts with the structure of polycyelo-phosphites.

It is known to "contain" in the manufacture of Esterer towers Polycondensation catalysts to "use the Make reaction conditions reasonable. Gravel "refers to gate all on a lowering of the * teakti onst temperatures or on a shortening of the steep times. Examples of such Catalysts with aromatic sulfonic acids such as p-toluenesulfonic acid » Aryl phosphate2 like trinhenyl phosphite, organic tin compounds vie dibutyloxotin and tfcrti ^ re amines vie Triethylamine. A lowering of the heating temperatures is achieved by causes such catalysts to varying degrees.

Admittedly, one of the serious disadvantages in Faufgenosien must be denied, which even precludes the use of the listed catalysts in some cases The use of aromatic sulphonic acids as a catalyst in the manufacture of ester-like poly-condensation products always leads to products with a dark brown color, for example.

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Arylptospores have the disadvantage that they are easily hydrolytic columns. The phenol or substituted phenols released in the process produce acid-colored ones on exposure to air Products and also inhibit radical processes Processes such as the oxy & active drying of alkydherxes and the hardening of unsaturated polyester resins. Also are organic sense compounds for the production of such alkyd resins unsuitable for those acidic with unsaturated fat like Linoleic acid are modified because these alkyd resins have a brown color will. AuSerdera is unsaturated in the production Polyester resins in the presence of tin compounds have a noticeable effect Yellowing cannot be avoided when doing certain Polyols such as 1,2-propanediol can be used. Finally, amines ■ cause the products manufactured with their help to have a strong « ftf show inclination to pay.

Surprisingly, it has now been found that the discovery avoid all these disadvantages and, moreover, still have a · A number of toe advantages can be achieved if one as K «.t * ly * M; oren certain phosphoric acid esters are used.

The present invention is a ^ out »» r - Preparation of Estergruppen containing Polvkonden *% tion products with improved properties, in which ä ^ x9 condensate ioasreakt ion in the presence of polycvelisehen Phoepheri * - säureestern as reactive catalysts is carried out "which is either a polycvclische Have a structure according to the formulas (I) or (II) in which H ₁ denotes hydrogen or methyl and R ₂ ⁼ alkyl having 1 to 10, preferably 1 to 3 carbon atoms or mono- or polycyclic conversion products of the compounds of the formulas (i) or (II) components containing carboxyl or hydroxyl groups

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of the reaction mixture are.

R,

P-O-CHr-C-R

2 (I)

(II)

The invention also relates to those containing ester groups Polycondensation products, in the mono- orpdhrcyclisehe Phosphorous acid esters, which differ from the aforementioned cyclic Derive connections by splitting a ring into in an amount such that the phosphorus content is 0.002 to 0.7 rev. Percent.

The general method for making these compounds is known and has been reported by ^W .F. ^w adsworth and ^TJ .D. Fmmons in J. Am. Chem. Foe. Bk_ _t 61 ^ (19 ^ 2) and in F. Ftetter and KF Fteinacker in Chem. Ber. 8 ^, 1 + 51 (1952). Fie happens

t I

the easiest way is to convert zf of phosphorus! / »S ⁵ uretrimethyl ester with suitable triols or of cis-1,3,5 · - cyclohexanetriol with phosphorus trichloride.

The use of such bindings leads to products that in addition to an exceptionally light color, very good resistance to yellowing exhibit. In addition, the reaction times required to divide such resins are significantly shortened. This is especially important for drying or non-drying alkyd resins and unsaturated polyester resins. The possible uses these catalysts are not limited for such resins.

Another decisive advantage of the invention is that that they are incorporated into the resin molecules by reaction with carboxyl groups or hydroxyl groups. Due to the tension of the polycyclic system, one of the three P-O-

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Bindings attacked relatively easily, causing the defrosting of the catalyst takes place in the resin. That at least The compound formed containing a ring is very stable. No undesired reaction products are produced during this installation educated.

All other properties of the resins, such as drying or curing properties, optical clarity, pigment wetting properties, Adhesion properties, oil, surface properties etc. practice those used in the present invention Catalysts do not have any negative effects.

The catalysts are generally used in such amounts that the phosphorus content in the batches is between 0.002 and 0.7%, preferably between 0.005 and 0.3% by weight of the resin formulas. The temperatures used in the preparation of the resins can preferably be between 150 and 250 ⁰ C and 270 ⁰ C 100 interlocutory.

The addition of the catalysts can before and / or during the The course of condensation take place in one or more portions. The catalysts, which are solid, crystalline compounds at the level, can be solid, molten or in solution can be used. When producing resins by means of an azeotropic distillation, the catalysts can e.g. Entrainers are dissolved. The catalyst can also be dissolved in a reaction component. Production takes place of the resins in reaction stages, e.g. in the case of half-estates, Transesterifications or isomerizations, "the catalysts added before or during or after such a reaction stage as long as they participate in at least one stage. Furthermore, the catalysts can also be used after the reaction with

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Polycarboxylic acids, hydroxycarboxylic acids or polyvalent alcohols admittedly verden.

It is recommended to use catalytic converters asleep very wherever there is tob products with manufacturing particularly light color arrives. With unsaturated polyester resins is the3 the case, for example, with highly translucent laminates, such as it is required for translucent corrugated roofs or light domes verden. Even with alfcya resins, a light color is always an advantage, because then the setting of a certain color tone is at the manufacture of varnishes is particularly easy »e.g. leads in production a light blue autorepsraturlaekes too dark a color of the used alkyd resin to a greenish hue.

In the following examples, T means parts by weight.

Examples

1) 360 T phthalic anhydride, 332 T pentaerythritol, T2U T benzoic acid, Ilk T p-tert-butybenzoic acid, 5 ¹ ^ OT soybean oil fatty acid and 50 T xylene all seafood were at 210 ° C with exclusion of air in the presence of 1.5 parts lt-Ä "ethyl-1-phospha-2,6,7-trioxy-bicyclo [] _2,2,2j -octane (see formula (I)." with T? _t »H, P ₃ * C ₂ E ^ carried out,! times a reaction time of 50 hours, an alkyd resin was obtained with the following properties: Viscosity (according to Ubbelohde, measured at 20 ° C in a 50% solution of white spirit / xylene 3: 1} of 3,900 cP, an acid number of the solid barze (DIK 53 I83) of 6.8 and an iodine color number of 2, measured in 50% solution according to DIB 6t62.

Verftl "I" example A) : When the approach was repeated without addition of catalyst, an alkyd resin was obtained after a reaction time of 17 hours with a viscosity (measured as before) of 3,600 eP, an acid number of the solid resin of 5-8 and one Iodine color number of 10 (measured as before) was obtained.

Comparative Example B) : The esterification of the batch according to Example 1 was carried out under the same conditions in the presence of 1.5 parts of p-toluenesulfonic acid. After h hours the batch had turned dark brown, so that the experiment was terminated.

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^ ergleiehsbeigiai el Γ); The esterification of the approach scemSS Example 1 was carried out under the same conditions in the presence of 1.5 T dibutyltin dilaurate. To. 8 hours, an alkyd resin with a FIskosit ^ t (measured as above} tos 3 500 eP, an ^ acid number of the ^p est resin of 7.3 and an iodine color number of 25 (measured as before) is obtained.

2} 770 T of linseed oil, 375 T of pentaerythritol, 185 T of benzoic acid, 1 * 30 T of phthalic anhydride, 25 T of petroleum as a chemical were "at 2 ^ 0 ° C in test of ° parts of ethyl i-tihosTiiia-2 »6, t * rioxa-bicyclo \ _2 ^ _y 2,2 octane esterified Luftaussehluß. after a reaction time of lh hours an alkyd resin with a ^Tr iskosit" t (measured after tTbbelohde, FCO tift in Tesfbenzin at 20o c) of 330 cP, a Rpure number of the solid resin of 5 and an iodine color number of 3 obtained.

yergleiehsbeispiel P): is the same approach accordingly, but esterified in the absence of catalyst, one erhSlt after a reaction time of 20 Ptunden an alkyd resin with a Tiskosität (measured as in Example 2) of 35D cP, one of the solid resin of 3 and an iodine color number from 11.

3) TSO T linseed oil, 230 T pentaerythritol, 28 T aivcerin and 3 T benzoic acid were transesterified at 270 ° C. under a protective gas atmosphere of nitrogen until a sample was clearly miscible "with any" amount of ethanol. Then the temperature was lowered to 220 ° C, after which U03 T phthalic anhydride, t _t 6 parts of k-ethyl-1-phosphe-2,6,7-trioxa-bicvclo C 2.2.2 J _

octane and 50 T xylene added as a drag agent and the Esterified approach at this temperature. Make a response time

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After 5 hours an alkyd resin with a vi (60 ig in enzine / ^ ethylene glycol mono-ethyl ether 3 ^: 2, "at 20 ° C) of _{3,200 cP, a PS ure number} de * ^ est resin of 11 and an iodine color number of U obtain.

Comparative Example F): If the same batch was reacted accordingly without a catalyst, after a reaction time of 7 hours an alkyd resin was obtained with a viscosity (measured as in Example 3) of 3,000 cP, a solid resin number of 15 and a dead color number from 12.

k) to 6) In several batches, 9 ^ 2 T maleic anhydride, 776 T hexachlorodotnetirvlentetrahvdrophthalseure, 2Q £ T 'phthalic anhydride, 1003 T 1,2-pronanediol with the addition of UOO T xylene as a chemical to 100 ° C heated "until the half-figure was completed. This

f »

can be recognized by the subsiding of the exothermic reaction, what after 35 to UO minutes was the case. This half-Christian was now optionally acc

Example k with 3 T U-methyl-1-phosphate-2, ^, 7-trioxa-bicyclo J2,2,2j -octane,

Example 5 with 3 T 3-methyl-U-S.thvl-1 -phospha- 2,6,7 ~ tf ioxa-Mcyclo p2,2,2 J ~ octane,

Example 6 with 3 T of the ureas substitution product from 1 mole of U-Xthyl-

1-'phospha - 2,6,7-trioxa-bicyclo Γ 2,2,2j-octane and 2 moles Succinic acid,

Comparative ^{example v} ) with 3 parts of ^rp riphenylphosphite, comparative example G) with 3 parts of dibutyl oxo-tin and in each case to 172 ° within one hour. C. heated, at this temperature the reaction mixture was under

7 *

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azeotropic separation, the water of the egg kept so long, "until an i ^ ure number of 1B was reached. Then it was the temperature increased to 18O C and under ^ acuum (approx. 20 mm Fg) the towing agent unfl excess! res propand-ϊ ol-1, 2 distilled off. Thereafter, after cooling to 130 ° C., t IU5 parts Rtvrol stirred in. In all ^ llen there were about 3 ^ un parts Polyester-Ptvrol-Temisch obtained.

The following table shows the main oats of the rait various catalysts produced unsealed Polyester juxtaposed.

Reaction time to SZ »18

Color number +)

Viscosity +) (20 ° C)

Pot life ++)

Color of the hardened polyester

i | h Uh U, 5 h 8, Hh ^ 1 <1 1 - 2 - λ 3

U200 cP l + ooo cP Uonn c

12 '12' 12 '

ocP k% on _c p

"1 1" 30 "

-nrakt-i sch ■ '' arblos- yellowish a; eli!>

+) measured on the undiluted, containing approx. 30% styrene

mixture

++) after the addition of '1 < MethvlSthvlketon ^ roxvd 5C? ip: and 0.5 Io VanaÄi n acceleriprer 0 2 d der ^ irna Oxido

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If the same batch condenses without catalysts, it is only possible to achieve _{the desired s5 U} values at considerably higher reactivity temperatures (200 to 210 C). Such a polyester is, however, apart from the likewise unsatisfactory fineness (iodine arbznhl> ^), not faded with the * n the examples k to 6> ar, because it is originally sm ⁵ °> i p. higher skosit ^v i ^s th comprises (^ 6000 cP at 20 ° C).

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Claims (1)

Claims 1) '''"learn about Ferstellune: of containing ester groups
Poly condensation products with improved properties • characterized by the fact that the
.Kondensationsreaktion is NHRT in ßeitenwart of cyclic PhosphoriggSureestern as reactive catalysts durchpe ^ which either e ⁿ 'ne Tiolycvcli.sche structure oiera ^ R ^ Ormel (T) or have (TI), where ^p .i ^TT a <3ser sto ^p f or ^ ethyl and Rp are alkyl having 1 to 10 carbon atoms ", or
mono- or "nolvcvali see _Umsetzunsr; sprodukte the ■" containing KomOonenten 'onnectivity the "Ornel (T) or (Tl) nit CarTioxyl- b7.w. Hydroxylfrruppen of ^ ^ eaktions emisches are. I P 0 — CH _χ // \ 2) Method according to claim 1, characterized , because the phosphorus content 1 of the catalyst line 0.002 to 0.7 ^ ew. Percent of Farzrecipes is. 3) ^ out by Ans-nruch 1 or?>, Characterized in that the ^p hosphorantei'1 fle · * catalyst is 0.005 to 0.3 wt. Percent of the Farzrezepte. / 11 409834/096 U) Estergruppen Polvkondensat containing i onsrcrodukte characterized in that mono- in them or "Dolvcveli see Phosnhori ^ s ^ acid esters are condensed, the onnectivity from the pennnnten in claim 1 cyclic ^ by Aufsüaltunsr one or more ^p INPE derive such a ^ enee that the phosphorus content is 0.002 to 0.7 "• ev, percent January 31, 1973
Dr. k / he A0983A / 0966