DE2308802A1 - PROCESS FOR THE PRODUCTION OF HARDABLE COMPOUNDS - Google Patents

Description

"Process for the production; hardenable masoen"

The invention relates to a method for producing curable Masses by mixing one or more Polyisocyanates with an amine and a li> oxide. The invention also relates to the use of the manufactured according to the invention hardenable masses for the production of moldings, v / ie GießiJn * - genes and laminates. The masses can be used very cheaply as impregnation resins be used.

Me use of epoxides as coinitiators in the polymerisation of organic I: .0C3 ^? anate to polyisocyanates, which is initiated by tertiary amines is disclosed in US-PS 3,168,483

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described.

It is known that polyisocyanates which have been obtained from aromatic diisocyanates have good hardness, are flame-resistant and mechanically stable at relatively high temperatures, for example 180.degree. However, they are generally brittle, as a result of which their possible uses are considerably limited. In addition, at temperatures above 200 ^° C., the thermal stability leaves much to be desired. At these temperatures, the polyisocyanurates begin to decompose, which is accompanied by the formation of cracks and foam. The mechanical resistance at elevated temperatures of polyisocyanurates obtained from aliphatic diisocyanates :! have been obtained is so small that objects made therefrom are generally of little practical use.

In DT-OS 2 060 600 a process for the production of polyurethanes is described, starting from one organic isocyanate and one having a molecular weight from 700 to 5,000, which is a reactive hydrogen atom must contain, in the presence of an epoxy resin ^ and a curing agent to be selected from diolines containing primary ikmin groups or hydrocarbons with 2 to 6 carbon atoms, containing terminal Hydroxyl groups.

It has now been found that when an olefinically unsaturated compound is added, the polymerization of a polyisocyanate occurs in the presence of an amine and an epoxide as initiators leads to products that are fully cured

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the can, whereby the stability of the products obtained is improved. At the same time has the addition of a unsaturated compound has the advantage that the flowability (fluidity) of the masses is increased, so that they are easily as Impregnating resins can be used. At the same time, the mechanical and electrical properties are like that thermal stability, of the products obtained in this way very favorable, especially if the epoxides used Are glycidyl ethers of diphenyl / propan.

The invention therefore relates to a method for the production of curable compositions by mixing one or more several polyisocyanates with an amine and an epoxide, which is characterized in that at least one olefinically unsaturated compound which is not an active hydrogen atom contains, adds to the mass.

Both aliphatic and aromatic polyisocyanates can be used can be used as polyisocyanates. Aliphacic and aromatic polyisocyanates are defined as compounds in which the isocyanate groups are attached to aliphatic or aromatic groups are bound.

Aromatic polyisocyanates which can be used advantageously for aas process according to the invention are, for example, m- and p-phenylene di-isocyanate, toluene-2,4-di-isocyanate and toluene-2,6-di-isocyanate, naphthalene-1, 5-di-isocyanate, Dipbenylmethan- ^ V-di-isocyanate, triphenylmethane-4,4 ^1, 4 "-triisocyanate, and mixtures of these isocyanates.

Examples of suitable aliphatic polyisocyanates are

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Butane - '], 4-di-isocyanate, hexane-1,5-di-isocyanate, 2, 2 , ^ - Tricot hexai-di-isocyanate, dodecane-1,12-di-isocyanate. Cyclohexsndi-isocyanate, dicyclohexylmethane-V-di-isocyanate, 2-butene-1,4-di-iGOcyanate and diethyl sulfide-S ^ '- di-iGocyanate Mixtures of aliphatic polyisocyanates and mixtures of aliphatic and aromatic polyisocyanates can also be used with advantage . It is preferred, aromatic polyisocyanates _(besocders those with an alkylidene between two isocyanate-substituiertcn Arylkerncn _t verv;. End Very good results were obtained with Liphenylraethan - <- f, V-diisocyanate.

The mechanism of the polymerization reactions leading to the superior polymeric products from the invention Leading the masses is not entirely clear. Anionic polymerization of the olefinically unsaturated ones presumably occurs Compounds since the presence of a peroxide in the raw material is not required to have a good To achieve polymerization of the existing fees., if there is an ainine and an epoxy "

Amines can advantageously be used as "anionic" initiators. Tertiary amines are particularly suitable. Examples of suitable initiators are triethylamine, pyridine, triethylenediamine, Diaethyläthanolaain, hexa- 'hydrodimethylanilin, Benzyldiraethylamin, aI ^l Iethylben.zyldimetliylamin, N-Hethylpiperidin ur: d K-riethylaorpholin. Yorzu,.:, - wise become Beiizyldimethylajain or α-I'Iethy 1 benzyldii;: ethyl ^ r:.:. > \ used. In general, the amines are used in amounts of 0.05 to 5 mol / I, calculated on the polyisocyanates. If necessary, the initiators can be used in suitable solvents. Examples of ^ ceigneLe

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Solvents are methyl "oxitol", ethyl "oxitoi", butyl "oxitol" and dialkyl "oxitol" ^: ("oxitol" is ethylene glycol] monoethyl ether -O ·

The epoxides used in the process according to the invention act as very good coinitiators for the polymerization. Epoxides which are soluble in the used polyisocyanate are particularly preferred. Examples of suitable epoxides are monoepoxides, such as epichlorohydrin, propylene oxide, ethyl glycidate, butyl glycidyl ether, phenyl glycidyl ether and polyepoxides, such as diglycidyl ether of diphenylol prepane. Phenylglycidyl ether is preferably used as a coinitiator, as it is thin under the reaction conditions. In general, the coinitiators are used in an amount of at least 0.05 Mcl-%, calculated on the polyisocyanates. Greater than 5 %, calculated on the polyisocyanates, are generally not required, but can be used. In general, the initiators and coinitiators are present in approximately equivalent amounts, that is to say for each mole of initiator at least 0.5 KoI of goinitiator are present. Coinitiators are preferably used in amounts of 0.8 to 1.5 moles per mole of initiator.

Epoxides that also contain hydroxyl groups can not only be used as coinitiators, but also as Reactants for making resins by combining these compounds with a polyisocyanate and an unsaturated compound in the presence of an amine, preferably a tertiary amine. Examples for epoxies, which are very suitable for the

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Diglycidyl ethers to be used in accordance with procedures of diphenyipropane. The epoxides are usually used in amounts of 10 to 75% by weight, based on the amounts used Polyisocyanates are used. Amounts of 25 to 50% by weight, based on the polyisocyanates, are particularly favorable.

If necessary, coinitiators such as pivalolactone can be used and carbamic acid esters such as the ethyl esters of phenylcarbamic acid to be added to the epoxides. The acid esters can also be formed in situ if a Compound containing one or more hydroxyl groups, such as benzyl alcohol, for the polyisocyanate to be used is admitted.

As olefinically unsaturated compounds which contain no active hydrogen atoms, vinyl-substituted aromatic compounds and derivatives, especially esters, of acrylic acid or methacrylic acid can advantageously be used in the process according to the invention. The unsaturated compounds contain no active hydrogen atoms, as determined by Zerewitinoff (Weygand-Hilgetag, Organic-chemical Experiaen "cierkunst, 3rd edition, pages 1046-8). Examples of vinyl-substituted aromatic compounds that should be mentioned are styrene, ex-methyl styrene and styrene derivatives containing aiiien "or more inert substituents on the phenyl nucleus, such as methyl, ethyl, phenyl and like groups. Examples of suitable derivatives of acrylic acid are methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl acrylate, acrylonitrile and other compounds. Preferred olefinically unsaturated compounds are styrene, α-methylstyrene, methyl methacrylate and 2-ethylhexyl acrylate.

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Ira general will be the unsaturated ones mentioned above Compounds in amounts of not more than? 0 wt .-> j, based applied to the polyisocyanates used. The use of larger amounts of unsaturated compounds can under the heaktionsbedingungen to the formation of softer and lead to less good products. Preferably, amounts of 15 to 65 wt .- / ό, based on the polyisocyanates used, applied. In particular, the use of styrene in an amount of 25 wt. Iw, based on the polyisocyanate, to a product that is particularly suitable for manufacture from Gießlingen.

In a preferred embodiment of the inventive device In addition, an olefinically unsaturated one is used Compound containing one or more hydroxyl groups, too added to the mass. Acrylic esters containing one or more hydroxyl groups, such as Hydroxyethyl methacrylate and the reaction product of acrylic acid and the glycidyl ester of alkane monocarsonic acids, especially glycidyl esters of α-branched Alkaioiaonocax'boacoo.r ■, -! · with 9 to 11 carbon atoms and acrylic acid,

If hydroxy-substituted olefinically unsaturated compounds are added to the compositions according to the invention, the weight ratio of such compounds _c to the olefinically unsaturated compounds which do not contain an active hydrogen atom is preferably 1: 9 to 4: 1 and especially 1: 4 to 4: 1 and most favorable 1: 1, especially when a mixture of styrene and the reaction product of acrylic acid and a glycidyl ester of a cx-branched alkane monocarboxylic acid with 9 to 11 carbon atoms is used.

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The mixtures prepared according to the invention can be finer non-reactive components such as solvents, fillers, pigments, dyes, fibrous materials, such as glass linen and fiberglass and extenders such as asphalt bitumen, coal tar and aromatic extracts from Petroleum distillates or polymers such as polyvinyl chloride contain.

When using the mixtures according to the invention, ie when producing moldings such as castings and laminates, good curing, for example at elevated temperatures, is of great importance. Usually, the temperature is increased over time to at least 10O ⁰ C, with cure temperatures may be employed up to 20O ⁰ C.

The castings and laminates produced in this way have a very high thermal stability, which is somewhat higher than 250 ⁰ C. This property and the fact that the Gieilingc and laminates are generally hard and clear, making them particularly suitable, eg for shipbuilding, as Insulators and for printed circuits. The clarity of the products can often be increased by relatively small variations in the composition of the initiators and, for example, by adding small amounts of phenol.

The invention is further illustrated by the following examples, some of which are the limits of what is suitable Specify ratios or reference weights.

B is ρ i el 1

A mixture was prepared from two parts by weight of di-

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phenyl methane-V-di-isocyanate (MDI) and 1 part by weight styrene. 2% by weight of phenyl glycidyl ether (PGE) and 0.3% by weight of benzyldimethylamine (BDMA) were added as initiators. After one hour of curing the mixture at 80 ⁰ G and then for 1 hour at ⁰ C 15Q hard, cloudy castings were

the '

obtain. It showed that a peroxide was present had no effect on the polymerization.

example

The polymerization of a mixture of 4 parts by weight t _e ilen MDI, 1 part by weight of the reaction product of acrylic acid and the glycidyl ester of "Versatic" -acid (ACE) and 1 part by weight of styrene with 2 wt .-% PGE and 0.3 wt% BDMA introduced. The ^w Versatic "-acid was a mixture of mainly a-double-branched Alka nm onoc arb onic acids having 9 to 11 carbon atoms. After I6stündigem curing at Haumtemperatur and then for 3 hours at 180 ⁰ C to give a clear hard casting. Seemed At room temperature a Trimeiisierung After curing at room temperature, the infrared spectrum shows that the styrene was completely polymerized and the ACE was almost completely polymerized equivalent amount of phenyl isocyanate was used No polymerization of styrene was observed under these conditions.

Increasing amounts of styrene in the starting material from 1 part by weight to 4 parts by weight or 9 parts by weight under otherwise identical conditions resulted in good after implementation

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Castings · Addition of such an amount of styrene to the mixture having the original weight ratio of 4 MDI: 1 ACE: 1 styrene, which weight ratio was 4: 1:50 or more, resulted in a very good after curing for one day at room temperature soft gel-like substance and after 3tägigem baking at 100 ⁰ C was soft nan · turbid products.

His of the mentioned mixtures cured at tree temperature in the absence of an initiator. Moreover, was a mixture of 50 wt .-% styrene and 50 wt .-% ACE without isocyanate, which was started yet low viscosity with 2 wt .-% BDMA, with or without an equivalent amount of phenylglycidyl ether, after 3tägigem heating to 100 ⁰ C.

Example 3

4 parts by weight of MDI, 1 part by weight of styrene and 1 part by weight of ACE were mixed and 2 parts by weight of PGE were added. Various initiators were then added. The initiators used and some properties of the castings obtained are given in Table A. It was cured for 2 hours at 80 ⁰ C, 1 hour at 100 ⁰ C and finally 3 hours at 180 ° C.

TABLE A:

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TABEL

Polymerization of MDI / styrene / ACE blends Casting Ver
search initiator Wt% clear, proportionate
soft 1 - - clear, very hard 2 BSHA 0.3 clear, proportionate
soft 3 Dicumyl peroxide 0.1 clear, very hard 4th BDMA +
Dicumyl perbxide 0.1)

The casting of the experiment 2 had a Barcol hardness of 45 to 50 and a Vicat softening temperature at 0.1 mm penetration of 18O ⁰ C, at 0.2 mm from 205 ⁰ C, at 0.5 mm of 230 ° C and at 1 mm from 240 ° C.

The cured products of Runs 2 and 4 contained very small amounts of residual isocyanate. Apparently Good NCO trimerization occurs under the conditions chosen while no peroxide is required to polymerize the unsaturated monomers.

In another experiment, the mixture of MDI / styrene / ACE in a weight ratio of 4: 1: 1, an initiator mixture of one% by weight of PGE and one% by weight of BDMA was added. After 16 hours Cure at room temperature, then 1 hour at

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and 3 hours at 180 ⁰ C "of the cured product was in the form of resistance (heat distortion'temperature) 213 ⁰ G ,.

Example 4

Experiment 2 of Example 3 was repeated with the exception that a 4: 1 mixture of MDI and ACE was first heated to 95 ° C. for J> 0 minutes and then the same amount of styrene and catalyst were added to the cooled mixture. It was cured at room temperature for 16 hours and at 180 ^° C. for 3 hours. The casting obtained had a Barcol hardness of 42, a Vicat softening temperature of 0.1 mm Pen-

t:
250 ⁰ C and at 1 mm from over 25O ⁰ C.

tration of 176 ° C, at 0.2 mm from 215 ° C, at 0.5 mm from

Castings which had been produced from a mixture of MDI: ACE: styrene in a weight ratio of 4: 1: 4 approximately the same Barcol hardness and etv / as lower Vicat softening temperatures. The notched impact strength the castings are relatively low, namely 1.4 kg eaten according to the BS Izod method for castings from one 4: 1: 4 mixture and 1.1 kgcm / cm for castings from one 4: 1: 1 mixture.

Example 5

(a) Mixtures were prepared from 4 parts by weight of TIl) I, 1 part by weight of styrene and also 1 part by weight of ACE, ".Epikote" or ".Epikote" 1001. "Epikote" 828 is a reaction product from epichlorohydrin and diphenylolpropane with an epoxide equivalent weight from 175 to 210. "EPIKOTE" 1001 is a

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23C8802

The reaction product of epichlorohydrin and a diphenylolpropane with an epoxide equivalent weight of 450 to 525 · Bas ACE-containing mixture was made to polymerize with 1% by weight of BDHA and 5% by weight of PGE. The other two mixtures were made to polymerize with 1% by weight of a mixture consisting of 3 parts by weight of BDKA in 7 parts by weight of butyl "Oxitoi". It was 16 hours at room temperature, then cured for 1 hour at 150 ⁰ O, and finally 3 hours at 180 ⁰ C. The Barcol hardness of the castings obtained was 40 to 45. The temperature at which the castings were destroyed and some physical properties of the castings obtained from the mixtures given above are given in Table B.

TABE LLE B Notched impact Bend Starting Pormbe Blow strength strength mixed persistence firm (BS Izod: ζWeight Ver speed kgcm / cm K. kg / cm; ratio
4: 1: 1) ρ _ο) (BS-Izod:
kgcm / cm'v 20th 1330 MDI / styrene / 19o 0.7 ACE 18th 1330 MDI / styrene / 200 1.2 "IEpikote" 828 18th 1280 MDI / styrene / 220 2.0 "lEpikote ¹ x 1001

Laminates made from the above-mentioned mixtures

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had flexural strengths of 4,350, 4, and 4,550 kg / cm. In addition, the resistance was over 20 seconds contact with molten solder / girt. ^ Me laminates had excellent resistance to contact with boiling distilled water and a considerably low weight loss when exposed doors Tempera of 230 ⁰ C. After 3 weeks, the laminates with ACE were somewhat swollen, but the appearance of the laminates with ^IT .Epikote "828 was still good after 6 weeks.

(b) A mixture of 4 parts by weight of MDI, 1 part by weight of styrene and 1 part by ^{weight of "f} Epikote" 828 was started with 3 parts by weight of a catalyst composed of 0.3% by weight> o α-methylbenzyldimethylamine, 1.6 wt .-% phenol and 1.1 wt .-> butyl oxitol was. the reaction mixture was cured for 3 days at room temperature to give hard castings obtained. After curing at 180 ⁰ C, the dimensional stability was for the, · hartea bright red casting 26O ⁰ C.

The Vicat softening temperature at 0.1 mm penetration was 230 ° C.

Example 6

Mixtures were prepared from 4 parts by weight of MDI and 1 part by weight of ".Epikote" 828, to which 1 part by weight of the monomers indicated in Table C were additionally added. The mixtures were started with 0.3 wt% BDMA. There are infrared spectra produced immediately after the Initiierong nachi6stündigem and curing at room temperature and after a further 3 hours of curing at 180 ⁰ C. The results

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the infrared measurements (showing the ratio of vinyl and Specify isocyanate groups after curing in relation to the original content) are summarized in Table C.

TABLE ■ L E C. TDI: toluene diisocyanate 1/4 after further
3 h at 180 ° C 1/5 Mass Weight
Ver
holds- / ■
after 16 h
at room temp. PI: phenyl isocyanate 1/4 Vinyl / isocyanate,
Initial initial
Vinyl isocyanate 1/5 nis Vinyl / isocyanate /
Beginning-beginning
Vinyl isocyanate n.b .: not determined 1/4 O 1/5 MDI / "Epikote" 828 /
Styrene 4/1/1 1/5 1/5 1/10 1/10 MDI / "Epikote" 828 /
α-methyl styrene 4/1/1 1/4 1/3 O 1/4 MDI / "Epikote ·" 828 /
Methyl methacrylate 4/1/1 0 1/4 1/3 n.b. MDI / "Epikote" 828 /
Acrylonitrile 4/1/1 1/2 O TDI / "Epikote" 828 /
Styrene 2.5 / 1/1 1/5 n.b. PI / "Epikote" 828 /
Methyl methacrylate 4/1/1 1

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From these results it can be seen that after a main reaction at room temperature, a subsequent reaction at 180 ^° C. is favorable if a polyisocyanate is used. The experiment with phenyl isocyanate clearly shows, however, that methyl methacrylate, which reacts very quickly in the presence of MDI, does not show any reaction in the presence of a monoisocyanate.

Claims

62XXIV

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Claims (15)

Claims 1. Process for the production of curable compositions by mixing of one or more polyisocyanates with an amine and an epoxide, characterized in that that one has at least one olefinically unsaturated compound which does not have any active hydrogen atoms contains, to which mass admits. 2. The method according to claim 1, characterized in ze i.chn e t that the unsaturated compound is a vinyl-substituted one aromatic compound preferably used styrene. 3. The method according to claim 1, characterized in that that the olefinically unsaturated compound is an acrylic or methacrylic acid ester, preferably Methyl methacrylate is used. 4. The method according to claim 1 to 3, characterized in that the unsaturated compound is used in an amount of 1o to 65 wt. -Fy based on the polyisocyanate. 5 · Method according to claim 1 to 4 »characterized in that that one also has an olefinically unsaturated compound with one or more hydroxyl groups, preferably a hydroxy-substituted acrylic acid ester, especially hydroxyethyl methacrylate is used. 309839/0840 6 .. The method according to claim 5, characterized in that the hydroxy-substituted acrylic acid ester used is a reaction product of acrylic acid and a glycidyl ester of an alkane monocarboxylic acid, preferably a monocarboxylic acid branched in << -position with 9-11 carbon atoms in the molecule. 7. The method according to claim 1 to 6, characterized in that that the polyisocyanate used is a diisocyanate, preferably diphenylmethane-A ^ '- diisocyanate. 8. The method according to claim 1 bia 7, characterized in that the amine used is a tertiary amine ₍ preferably benzyldimethylamine ^. 9 · A method according to claim 1 to 8, characterized in that one uses the amine in an amount of 0.05 to 5 mol? S _(. Based on the BsLyisocyanat _(. 10. The method according to claim 1 to 9, characterized in that the epoxide used is a monoepoxide _i, preferably an benyl glycidyl ether and especially a reaction product of epichlorohydrin and diphenylolpropane. 11. The method according to claim 1 to 10, characterized in that the epoxy in at least one equivalent amount used as the tertiary amine. 309839/0840 - 3 - 12. The method according to claim 1 to 11, characterized in that that the epoxide is used in an amount of up to 75% by weight, based on the isocyanate. 13 · Use of the compositions obtained according to claims 1 to 12 for the production of moldings or laminates. 14. Use according to claim 13, characterized in that that the mass is heated to a temperature of at least 100 ° C. 15. Use according to claim 13 »characterized in that that layers containing glass fibers are impregnated with the mass and then cured. ^62v 309839/0840