DE1959935A1 - Process for the production of unsaturated polyester - Google Patents

Description

J) RILSERUCH PATENT ADVOCATE MONKS 5 1 Q ζ Q Q O C REICHENBACHSTRSI I v3 0 Ό Ό OO

ΤΪΙ.263251

polio
R / S eh

Allied Chemical Corporation "New York, M. Y ₀ , USA

j} [Oi ιre n gtu * Production of unsaturated polyester (Anas message from patent application P 19 21 910.4)

The invention relates to a method of manufacture unsaturated polyester from a statistical difonktlo nailen Alkohoi, which by partial blocking of the alkoho-X The hydroxyl groups of tris (S-hydr oxy alley 1) isorates are found is preserved by esterification "

The tris (2-hydroxyalkyl) isocyanurates are trivalent Alcohols of the formula

HO-GH-OH
R.

in 'ief Γ. % if: 3efatoff _s MefcliylL odar Sfeh

■ C i? ä δ 2 8/1 8 9'2

Trls- (2 ~ hydroxyUfchyI) -isoGyaaumfe and selee are polyester known »For example,» Pafc «n & Sülirift are in the USA 3 086 9H8 TrIs = (S-hydroxyathyl ^ isooyanurate and its homologues and in the ÜSA-PatenSaehrlft 5 3 ^ 2? 8O a \ ss dieseii duipoh Implementation with terephthalic acid and isophthalic acid Polyester described.

The parent application relates to © in Vsrfelsrara sur Preparation <AEE © in the method of the present invention as vervienösfeeii statistically difunktionelleB Älkotei9ls _s consists in that a Tris-Cg »hydro3Eyalkya) * ISOSS | fanurat, atoms in each 2» Hydraxyalkylgrtipps 2 to 4 carbon contains, with 0.9 to 1.2 equivalencies of an honoring work »» BMur · ® veresterfe, s © daS eisi ^M blocki @ i? l5 © s JeQQjmmv & fc ** © seldom becomes ₀

Ea viurcle found that this © blocklertaa Ißoo ^ aiBMrate with a Polyaarbor & ßMura to unsaturated Polyas'Seim »g @ s @ t ^ fc can and the unsaturated Polyesfeßi »¥ © rnetgt can, w © fe @ i Oießharga from Siervorrageiider. WMnnefestlgkeit » Resistance to weathering and dyeing to be retained will"

The invention is based on the ancestors of the production of an unsupported polysate in ₁ , which is suitable for the production of a resin, by using an alcohol with a FolysarbonaMur © at an elevated temperature # where at least one of the feeid @ ia keaktlon participant is a © äfchylenisohc? Contains double bloom. The ¥ out is characterized gekennselohnet that "one sinen Suroh esterifying a Tris-C2" hydro3iyalkyl) -isoüyanurmts "in which each 2-Iftrdroxyalkylgi ^t" ppe 2 to 4 carbon © © Fe @ 53, with 0.9 to 1 2 equivalent g @ «9i @ hten of a monocarboxylic acid obtained statistically difunctional alcohol reacts with a folyoarboxylic acid, the polyarboxylic acid and / or by reacting with the

0 0 9 8 2 8/1892

Monooarbonshure resulting portion of the statistically difunctional Alcohol contains an ethylenic double bond.

The preferred statistically difunctional alcohol "i. the preferred blocked tris (2-hydroxyalkyl) isocyanurate is blocked tris (2-hydroxyethyl) isocyanurate.

The blocking of a hydroxyl group in the tris (2-hydroxyalkyl) isoeyanurate is necessary in order to obtain polyesters with the properties mentioned above. If no of the hydroxyl groups in the isocyanurate is blocked, the polyesters, for example, will not have the desired one Solubility or gelling property.

Esterifying a hydroxyl group can be 0 _fi 9 up to 1-2 moles of monocarboxylic acid by reacting the isocyanurate with about Squimolaren amount dch ".

Suitable monocarboxylic acids are alkanoic acids, such as formic acid, Acetic acid, propionic acid, butyric acid * pivalic acid, Caproic acid, pelargonic acid and lauric acid that are unsubstituted or can be substituted, for example, by alkyl, halogen, alkoxy or hydroxyl} aromatic acids, such as benzoic acid, Alkylbenzoic acids, alkoxybenzoic acids, halobenzoic acids and Nltroberizoesäyren. Of these, benzoic acid is preferred <= If the isocyanurate is blocked with one of these acids, the polycarboxylic acid used in the process of the invention must contain an ethylene double bond. Alternatively can one with an unsaturated aliphatic carboxylic acid with up to about 12 cabbage (Mist of fat omen, such as acrylic acid, crotonic acid and Vinyl acetic acid. the substituents such as alkyl, halogen, Can carry alkoxy or hydroxyl, blocked isocyanurate and used with a saturated or aromatic or an unresistant polycarbo-HaHux «uirgeaetat.

009828/189 2

The reaction is preferably carried out under an inert atmosphere, for example under nitrogen, with or without a solvent _; for example, in the presence of the ubiquitous solvents * such as benzene * toluene or xylene, as the reaction medium. The esterification takes place at an elevated temperature of, for example, 1βθ to 220 ³ S, preferably between 200 and 220T.

The use of a catalytic converter is not necessary! however, the usual esterification catalysts such as for example p-toluenesulfonic acid can be used.

The blocked xsooyanurate can if desired in the usual way Way, like by removing the solvent, by extraction, Crystallization and the like. Isolated and purified by recrystallization, trituration or other conventional methods. That isolated blocked isocyanurate can then be used to make a polyester.

The crude reaction mixture obtained by the process of the parent application can also be used for the blocked isocyanurate, and the polycarboxylic acid and the other agents required for the esterification can be added directly to this reaction mixture containing the blocked isocyanurate. The temperature of the reaction mixture is expediently ^{lowered to about 150 °} C., polycarboxylic acid etc. are added, and the temperature is then increased again in order to accelerate the esterification. -

The polycarboxylic acid can either be used as such or in the Form of their acid halide, for example the chloride, a low molecular weight dialkyl ester or its anhydride be used. If desired, a mixture of polycarboxylic acids can also be used. Usable Ethylenic unsaturated. Polycarboxylic acids are for example

. 0 098? 8./1 892,

Maleic acid, fumaric acid, tetrahydrophthalic acid Endobis-5-norl) ornen-2,3-dicariW5neS «r © and the isomeric Net! ^ Lbioyclo- (2.2> l) <- hO]» tAn-2 «3-did & s ^> bonaSureii . Of these, maleic acid is preferred. Even Pol ^ axfruisMugisn olm © äfchylenischa double bond can be used mvaem J @ öooh mui in this case, the isocyanurates dee by blocking with oar acid formed group containing one double bond, 2u these polycarboxylic the Benzoldioarbonsäur @ a as PhthalsSur-t "and TarephthalsMur ?, Trltnell acid, adipic acid, sebaoic acid and azelaic acid. Hv & h of these SMuran can be used and can even be particularly advantageous if end products * which have the desired properties that are achieved with Yarwsnaisng affsmstiaoheL '* or saturated polyoarboxylic acids "and also those" that can be achieved with ethylenically unsaturated polycarboxylic acids "are produced are supposed to. For example, when using a mixture of maleic acid and phthalic acid, moldings of particularly good * hardness and heat resistance are obtained *

For the production of the polyester, at least about. Preferably between 100 and 120 $ of the amount of hydroxyl sulfate equivalent to the amount of acid used should be used.

After the addition of Polye & ^ honsäure the mixture at-a TemperaSus "heated between © twa l $ Q * ma vorzugsviölse of 200 to 225 ⁵ C, until the desired Säurozahl achieved. Usually a 1st Sahire number below about OEO preferred "Jedeoa can under ümstMM © ^, d _u h. depending on which molecular weight eCTettaßeht let whatever use imae the final product that is to> a% a @! * fo WhQs pay e Säuro s erwiinseiht © än _e drives ¹ × whom öieie ^ fe © SFCI £ aas ^ © Falyes & er

OiJ 9 6 28/1892

Is an acid steel »wipe, stw® 10 us & d S ^ ₄ preferably between about 18 and gi,

For oils !! © rstfllraig d <tr polyester kssiis the bl © oki® ^ t® al® the only sseforwer & ispa? Alcohol versf @ ßsl @ t wa ^ äsn, oder'eiss part of it can öujpsh eissen sd # r föshrsre auaS alcohols srsefegfc wardeis _o 2> ®γ Ant; #il eggs total amount of mehCTJsrt IgQKa alcohol asi äsai l? L © © ki © Ffe @ si Isösy nux · 5 ösw, "^ or 5 $ * beaog-an aui 'the equivalent weight * au is, voraisgswsi ^ e & fo @ r -.- ianlgotsns about 20 ö®» ;. - ·; gu den As a modification effiiit ^ el ferwendeteis polyhydric alcohols, di @ neto @ n ü®m hloQkl®vt @ n'iBOQjam , include examples ^ ieise Eth5? lenglyk © l glycol, GIyserin, Fentaeapftlirit ₉ i, 1, i -T ^ iaiettiylolMfehan , i> i, ioTrim @ thy'iGlpropan, S © rMfc _s mannitol "bipentaerythritol" allphatisehe ct ^ -0i © l @ raifc 4 odö2 * 5. coal asfeoffa for example -Butanediol-1 ₉ 4 _9. Peutandiol-ä "5" ynd isafeyn-S ^ diol-ip ^, so »i © © yslisefee dläfksle, for example 2,2,4,4- ^ atrai% fchylrl» 2-oyelobuta3idiol _#

When such a modifier uses "polyhydric alcohol". will, so come θϊ ² d @ ja He®k% loasgei5iiseh sow! old the

™ remaining Kosip © nant © n are added »

Very gu% ® ErgebniSB® but ersielt AUOH when the PolysarbonaMwa swiaäehst a? It of blookiert @ n Xsooy & niirat tsilsitiiie verestsrfe and daim änlt a modifying Giykol vein ιηαΘί ^ ίϋ mshrw @ i ³ & ig @ ii alcohol vielter verestert- is _o in g © 2. @ hen two-step processes can use glycols or others

llköliolQ be of very different structure ^ mifw®uä®t . In general, the -but usually the production by-Fon polyesters Olykole used, especially © © M re Alkylesiglykole the Fornel..H (OR) OH, in der.η 1 or höher® whole MHI, preferably 1 to 10, and H is an alkyleri », dJi.

009828/1692

(MGtHAL

Polymethylene radical, for example di-, Trj- or tetramethylene, is used both if they are added at the same time as the blocked isocyanurate and if they are added at a different point in time. Suitable are, for example, ethylene glycol, diethylene glycol, Pr © _r pylenglykol dipropylene glycol, tripropylene glycol, TrlSthylenglykol, Batylenglykol, tetramethylene glycol, neopentyl glycol, 2-Mefchyl "l, 3-pentandjol, 1,5-pentanediol, and hexamethylene glycol.

Since the blocked isocyanurate containing an ethylenically unsaturated bond is in the mixture React lone expedient an inhibitor for the polymerisation vlny!, For example, hydroquinone, mono-t-butylhydrcchinon, etc. _u Bnnzoahinon used. Usually an amount of about 0.02 to 0.05 ow "-ji of this inhibitor is sufficient".

The polyester can by conventional measures, for example Removal of the solvent or solidification by cooling from the Heaktlonsgemissli isolated cards

Instead of using the two-step process described above, in which the blocked isocyanurate first; and from this the polyester is then produced, the production of the polyester can also be carried out in a one-step process, in that the polycarbonic acid is added to the isocyanurate at the same time as the monocarboxylic acid acting as a blocking agent, taking into account the ratio of the reactivity of the blocking agent and polycarbonate can by selecting the Reaktionstemporatur, the catalysts of the ReihonfoXge of addition, and other variables to be achieved in that a hydroxyl group of the trihydric alcohol used as a starting material is blocked by the Monooarbonsäure _o particular, steps must be taken zurüokzufUhren to volatilized monocarboxylic acid in the reaction vessel,

0 0 9 8 2 8/189? SAS

The unsaturated polyesters obtained when using an unsaturated polycarboxylic acid for the production of the polyester from a blocked isocyanurate or when using an unsaturated aliphatic monocarboxylic acid for the production of the blocked isocyanurate are suitable for the production of laminates, compacts and castings of high quality. For this purpose, the polyester monomeric crosslinking agents, for example styrene, α-methyl styrene, methyl methacrylate, diallyl phthalate, triallyl isocyanurate, trialyl cyanurate, ethylene glycol dimethyl aorylate and its homologues, diethylene glycol divinyl ether, alkyl vinyl ether, alkyl acrylates, etc., are added. Such masses are described in more detail in the patent application P (Folio 14458) of the same applicant from the same day (also separation from the parent application P 19 21 910.4). ,

By the choice of the blocking agents used Monoarboxylic acid can have hardness as well as strength at room temperature and increased temperature for a given degree of unsaturation can be influenced »The best hardness and Strength both at room temperature and at increased Temperature is, especially when using TrIs -. (2-hydroxyMthyl) isocyanurate usually obtained with benzoic acid. By using an aliphatic mono-carboxylic acid on the other hand, a polyester with greater flexibility is obtained.

It has also been found that by using glycol or another polyhydric alcohol such as propylene glycol, as described above, the properties of the cured or crosslinked polyester can be further improved, so that a particularly hard product or a product with particularly good strength can be added elevated temperature is obtained. For this purpose, the Beaktionsgemisoh for polyester "education are advantageously between about 10 and 16 Qew.- £, preferably 11 to IJ wt -. <$ ,, glycol added."

009828/1892

BADQRIGINAiL

1359935

The excellent properties of the cured polyesters of the invention include, in particular, their high thermal stability and heat resistance. The thermal stability, which results from the weight loss of a sample in a draft oven, increases as the amount of blocked xocyanurate in the polyester drum increases. For example, a polyester which contained 1 mole of blocked Trls (2-hydro3cyittsjr!) - isocyanurate, 1.1 moles of propylene glycol and 1.0 mole of maleic anhydride, lost about \ $> its weight if a? 50 hours at 80 ^ C "If heat-resistant polyesters are obtained, preferably at least about 0.9 mol and in particular about 1.1 mol of blocked xocyanurate per mole of polyearboxylic acid are used." Kthylenglykol, is preferably from 0.9 to 1 ₅ 2 moles per Koi P © ly © arben acid ₀ From BlnfIu3 on the heat resistance of the polyester and its initial content of äthylenisoh unsaturated Polyearbonsäure well as the structure of the monocarboxylic acids and the monomeric Ve let rnefe actant ο with increasing unsaturated he £ t the Hitzestabllität the cured polyester © takes below. A preferred Vernetzungsmifctel to l ^ ^ ng zlel giifeei ¹ H'tssestabllität 1st diallyl !, and Triallylis ^ cfanurat even better results. By using an aromatic mono-carbonic acid as a blocking agent, better heat stability is achieved than the usual use of an aliphatic acid.

Because of their excellent heat resistance, dia Polyesters of the invention especially for manufacture by GIe (3 λ Ingen and laminates, for example in the field electrical engineering at elevated temperature ·, for example can be used in switching devices, such as manual transmissions should.

0 098 28/1892

Furthermore, as the degree of unsaturation of the polyester increases, so does the ice resistance; the cured product increases] under circumstances so weife "tHe this selbsti ^ eshend 1st, when the Vernetssuiagsdiehte because of a verhältnismäSlg low content however, w ^ saturated Slisips is too low, hardened 'products are obtained with verhälfenisn-äiig low Plammfeafeigkeit * WSMI so the Plaaaafss & igkelt. The importance of the end product is, preferably, a relative importance. size. Mentge an un ^ sMttigfcer SHwe, like Malein = qü & p Ww & rBäum * ψ @ η vienigsteas atsa il- Gew _o - ^ and preferably about 20 Ost / »· = - !, based on the in the Keaktionsraediujn © ingebraehfea

used »ExampleBweisa tsramifc aln polyester with 14 maleic acid and &&% nitrogen only 3.81 mm with a speed of only 2 ₃ 2ß mtn / min, bestinrat gainäB ASTM 6-625-6: 5 * ηηύ is © oaiit as" self-loosening " sii beasiehnen. These themselves lus @ hestäi @ n. Folyes'eer are suitable lusbesonäere for © ins use lsi mus lementen as well as in systems for the military and navy and in "Krafti '

Another her? Os ³ ragencls property of ne ^ sesa polyester is its © .Witterungsb © stli-aiIi ^ c0l &, it is wslt tessser than that of materiallsnj, which hitherto has been rejected as se

© Rgss & hsn were. When nansh irradiation

". with W-Lloht ti © your energy HEiSer Conditionufsgesi'.high 'Feuehtigksit uiid at high ¹ temperature and frequent spraying with water other products -IMBgSS unasis @ lmli3h" got ija ^ an _s had the Polyasfeer ösf invention nui? vi-anig of ih ^^ i initial /

F ¹ Ur these "Itjssk Is Methyiiaethaerylat a preferred crosslinking agent since it that of the refractive index of Endproöiaktes in the sewing © van brings glass, if it in

009828/189 2

Mixture with styrene is used in a ratio of 50-50, polyesters with particularly good weather resistance are obtained. The amount of crosslinking agent oils, the polyester are admixed MU8 so that an improved WitterungsbeatandigfceIt is obtained la cheating generally between 30 and 50 percent by _e - #, and preferably between 35 and 45 wt .- ^,

The resistance to weathering of the end products obtained from the polyesters depends not only on the type and amount of unsaturation, but also on the isocyanurate content. The blocked isocyanurate content should be between £ 87 and £ 64 and the unsaturation (for example maleic or fumaric acid) content between £ 13 and £ 26, based on the weight of the polyester coating. Preferably between 10 and 16% by weight of a glycol or another polyhydric alcohol, such as propylene glycol, is added, in which case the upper limit of the isocyanurate content falls to between 77 and IVFL.

Other factors which, as the longest *? «**: influence the indiability of the end product, are the presence of UV absorbers, for example benzophenones and Benztrl & Eolen. Laminates that Containing large amounts of the polyesters have excellent weather resistance.

Because of the durability of the surface gloss, these Polyester can be used with advantage, for example, for the production of high-voltage insulators, as these Property for the prevention of flashovers and leakage currents is essential. By rollover and Leakage currents can lead to erosion of the surface and thus to a change in the shape of the insulator, which in turn increase the risk of overburden. Also takes one

009828/1892

BATH ORIGINAL

... 12 -

duroh weathering rough surface easily contaminates from the air «which in turn leads to conductivity and Risk of overshooting be increased.

The polyesters can also be used for the Alkydhars-Preemeesen Manufacture of high voltage insulators or for the Beretstellung of molding compounds for objects of high impact strength are used «as in the patent application mentioned P (Folio 14458) described in more detail.

The following examples illustrate the invention.

Babeispiel i

Polyesters from Trls ~ blocked with benzoic acid (2-hydroxy ~

ethyl) -laooyanurate and maleic acid -

Duroh convert 1 * 1 Hol Tris- (2-hydro3syäthyl) -isoeyanurat with 1.2 mol of benzoic acid as in Example 1 of the Stama application P 19 21 910.4 a benzoic acid blocked Txis- (2-hydroxyethyl) »leooyanurat was produced. As the acid number Was 26.0, the reaction mixture was cooled to 150 ^ 5, and 1.0 mole of maleic acid were added together with 0.02% weight Total amount of reactants added to hydroquinone.

The Oemisoh was heated to 210% within an hour and by means of a Brocket at temperature controller under a stickst of fet rom of 28.3 cnr / h and a stirring speed held at this temperature of 250 rpm. After 1 hour the acid number had dropped below 50. After that, the Rectlflkationekondensor removed so that all volatile Components have been removed. At this tent point were another 0.015 wt .- $ hydroquinone added, and the reaction was allowed to drain at 210% for another 3 hours until a PolyGBter with the desired properties was obtained. The polyester had an acid number of 16.0 and a hydroxyl number (mg potassium hydroxide per g sample) of 39.2,

Π Π 9 8 2 8/1892
_k , .BAD ORIGINAL

BelQpiel 2

By reacting 1931 * 5 g (7.40 mol) of triB- (2-hydroxyKthyl) "" isocyanurate and 99 * »5 g (QΛ5 MoI) benzoic acid, as described in Example 1 of Staamannmeldung P 19 Sl 910Λ, a blocked one was blocked Tris (2-hydroxyethyl) isooyanurate with an acid number of 26.1. Then the reaction temperature was lowered to 15OV "and 1452 / Og (14.8O Hol) maleic acid" anhydrite *, 620.0 g (8.15 mol) propylene glycol and 1.00 g (0.02 Sew. ~ £ of the charge) Hydroquinone was added. The temperature was increased from 150% to 2ICH: within 1 1/2 hours and then maintained at this value * The stirring speed was maintained at about 350 rpm and the nitrogen flow at 42.5 to 56.6 cnr / h. After the acid number had dropped below 50, the volatile constituents - * were separated off, and a further 0.075 g (0.015% by weight of the Beeohinon) hydroohinone were added. After 5 1/4 hours at 210 °, the product was cooled to 16OT and poured into dishes lined with aluminum foil. The properties of the polyester were:

Yield / % of theory 99.0 (50 pounds of solid in Sura number 19 * 2 Methyleellosolve) Hydroxyl number 52.5 MG (Number Average Hol.Wt.) 1565 Gardner-Holt bubble viscosity £) 5/4

A type of solid was added to 25 to 58.5% in diallyl phthalate with stirring, so that the diallyl phthalate content was 52.7% (equivalence of the ratio of aluminum group to maleic acid 2.8: 1). This solution (diluted viscosity Z ¹ ^) is mixed with 1% by weight of the resin solution of benzoyl peroxide in the form of a 50 # -igon paste in Trieresy! Phosphate and between ^ ertitsaX © steel coated with a polyvinyl alcohol film.

0 9 8 2 8/1892

and glass plates, slide were separated by a 3 »2 now thick distance stucco Teflon» poured For curing of the resin, the mold was heated in a Luffczugofen hours at 50 <€ and then 2 1/2 hours at 120 to 125 ⁰ C. The thus obtained Giefll rings were tested for the endemic stability by using, as puncture of the tent were the "weight loss in a Luftzugofen at 8O ⁰ C and at ¹ 2 K) ⁵ C bestimmteV the results:

ßCPC Islfc (Stdn,) 1 -4 7 31 54

% Weight loss 0.68 0.79 0.97 1.02 1.13

240 * C time (hours) 12 19 27 91

% oil loss 7.5 12.0 32.5 37Λ 50.7

Ex iel

The procedure of Example 2 was repeated "by." 287.1 g (1.10 mol) of tris (2-hydroxyethyl) -13ocranurate with 127.6 g (1.10 hol) Caprona acid to a statiatlach dlfunktlonellen Tris- (2-hydroxyUthyi) -Isoeyanurafc were langaaetzt. After the number of blocked tris (2-hydroxyethyl) isocyanurafcs The reaction temperature dropped to 21.6 watv lowered to 153 "C, and 37.0 g (0.25 mol) phthalic anhydride, 73.5 g (0 * 75 moles) maleic anhydride and 0.1845 g {0.035 ßevi .- ^ of Baschiokung) hydroquinone were added * The obtained Pelyestsr had the following properties:

Yield, t d »theory 92.0

acid number 18> 9

liydrojcylaahl 46.7

MO 1710

Gardner-Holt pale viscosity D-E {5056 solids in

Methylcellosolve)

009828/1892 ORiGINAL BATHROOM

So much styrene was added to the product to make a solution with 21 * styrene (molar ratio styrene! maleic acid 2.8: 1) was obtained. This solution was as in Example 2 with Benzoyl peroxide mixed and hardened.

A piece of the clear Qiesslinga obtained was gemKfi ASlW D-635-63 tested for flammability: Brenngesohwlndlgkelt 2.26 mn / nini burned distance jj * 81 mn. I.e. the qiefiling was odor-quenching.

Example "

Following the procedure of Example 2, polyesters of im the following specified composition prepared. These polyesters were treated with the specified crosslinking agent !! insufficiently so that Qie resins were obtained.

0 Q H; H .-- ipq?

BAD ORteiNAU

: 4 »

to

- 16 -

CVi

co

ft

CVI

CV] «-

GO 00 SUN

• ft ft

CV Ol CU

© φ

ft 03

I!

03

N § h VQ

* ρ f vS

CU Cy CU * · »" CVi

M A (O IA O Μ <A I ^

OS O W

• ft «

CVl

CM * VO tß

<»· Ft

OV OV Ο 4 p * J *

· - «-w W wcvjcvi

OO

• A Wk ft »« ft * »»

ft

ft

CVl 0 0

0 ft

S S SS S S

ft T- ft « ¹ - ft« ~> * ft

CVI CU ft ft

8 ^a 8

β «

O «O« i © »O ·» O · "Ol * KS

Γ Ρ9ΡΡ8 / 189?

BATH ORIGINAL

T = »tris (2-hydroxyethyl) isoeyanurate

BS η benzoic acid

NS «nonanoic acid

DAG a diethylene glycol

NPO »Neopentyiglycol

PO β propylene glycol

MA s maleic anhydride

PA »β phthalic anhydride

AS * adipic acid

STY β styrene

MMA = i methyl methacrylate

DAP «diallyl phthalate

* plus 1} 5 benzoyl peroxide (as a 50% paste in Tricresylphoephate)

D09828 / 1892

ORIGINAL

Example £

A tris (2 ~ hydiO: xyethyl) isocyanurate blocked with benzoic acid with the acid number 25.8 was produced, as described in example 1 of the parent application P 19 21 910.4 * The reaction mixture was then 6o8.4 g (6.20 moles) maleic anhydride, 918.8 g (6.21 moles) phthalic anhydride and 519 * 2 g (6.82 moles) of propylene glycol Esterified according to the procedure of Example 3. The polyester obtained had the following properties

Yield, % ti »theory 97 * 9

Acid steel 20.2

HydroxylsahL 20.2

MG 2780

Gardner-Holt «SlasenvlskoB it St F? / ¹ * (50 ^ Festetoff in

Mefchylcellosolve)

This polyester was used for the production of molding compounds used for objects with high impact strength,

0 0 9 8 2 8/1892

Claims (1)

Claims 1oi process for the production of an unsaturated poly-Wtere, which see suitable for the production of a resin, by! preparation of an alcohol with a polyearboxylic acid at an elevated temperature, at least one of the both reactants contains an ethylenic double bond, characterized in that one is obtained by esterifying a tris (2-hydroxyalkyl} isooyanurate in which each 2-hydroxyalkyl group contains 2 to 4 carbon atoms, with 0.9 to 1.2 equivalent weights of a monocarboxylic acid obtained randomly converts the functional alcohol with a polycarboxylic acid * where the polycarboxylic acid and / or the proportion of the statistically difunctional alcohol produced by reaction with the monocarboxylic acid is one Contains ethylenic double bond. 2 * Process according to claim 1, characterized in that 67 to 64 wt Statistically functional alcohol with 13 to 36 -Ji converts the polycarboxylic acid. 3 · Method according to claim 1 or 2, characterized marked without the fact that one instead of a Part of the statistically difunctional alcohols used another polyhydric alcohol. 4 · The method according to claim 3 # thereby ge « indicates that one has 77 to 64% by weight the randomly unsaturated alcohol and 10 to 16 wt .- ^ of another polyhydric alcohol with 13 to 36 £ converts to the polycarboxylic acid. '.8 H 2 BAO ORIGINAL 5 · Process according to claim 3 or ^ thereby gikannsil eboi t »that nan a Qealseh of the statistically difunctional alcohols with an olycol of the formula H (OR) _n OH * in which η 1 to 10 and R converts a poly-1st» old of the polyacarboxylic acid . 6 · Process according to Anepruoh 3 WLa 5 » characterized in that the olymol or the other polyhydric alcohol is added to the reaction mixture after some of the polyoarboxylic acid has reacted. 7 · Procedure according to claims 3 to 6, d u r c h Gektnnseiehnet, 'that one 77 to 64 Oew.-Ji to the statistically functional alcohol in which one hydroxyl group old benzoic acid is esterified «and 10 to 16 dew .- * anea Olykol old 1? up to £ 36 wt Nalelnsllure uasetst. 8. Procedure nseh a dtr. previous claims « d 1 d u r ο h fiitianiilrachtti that one the statistic difunctional alcohol converts »without suvor from the solution in which he is formed isolate· 9 · Method according to the preceding claims « characterized · that aan a Oealsoh the PolyearboneKur © with the tria- (2-hydroxyftlScyl) -isoeyanurat and the Monooarbonslure «from which the statistically difunctional alcohol derives «on one Temperature at which the esterification takes place «heated» and evaporated monoarboxylic acid condensed and into the Response time is guaranteed. 00 98 28/1892 <ii.3O ■ '- 10, the method according to any one of the preceding claims, characterized in »that one used as the statistically difunctional alcohol esterified with the monocarboxylic acid tris (2-hydroxyethyl) isooyanurate. 11. The method according to any one of the preceding claims characterized in that one a tris (2-hydroxyalkyl) isooyanurate esterified with benzoic acid as the statistically difunctional alcohol used. QQ9828 / 1892 ORIGINAL