DE1570961A1 - Thermosetting resin compound - Google Patents

Description

M 1712

Minnesota Mining and Manufacturing Company, Saint Paul,

Minnesota 55101, V.St, A.

Thermosetting resin composition

The invention relates to thermosetting resin compositions, which in Liquids that flow freely at room temperature, but when heated to a moderate degree they turn into a viscous, flexible, cure thermoset state. Compared to known resin masses, which cure to a pliable state lead to the invention Masses of products that have unusually good electrical insulation properties at high temperatures and at have high humidity.

Electrically insulating casting resins should be sufficient have low viscosity so when pouring into a Form that contains an electrical component or device, all spaces in the component or device are filled. The resin should usually be free for more than an hour remain flowing, but should increase rapidly with moderate heating

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cure to a sufficiently tough, adherent state to be able to withstand thermal and mechanical shock effects to which the cured product may be exposed during its use, while at the same time having good electrical insulating properties under potentially adverse conditions. Resins that meet these requirements have been commercially available for many years. To date, however, no resin has been developed which ^{would meet "Class I" 1} conditions, that is, which would be suitable for continuous use at 155 G or above, although long-term efforts in this direction have been made.

These conditions are now met by the thermosetting resin compositions according to the invention, which are conveniently brought onto the market in two parts, which can be stored for an indefinite period of time under normal storage conditions. In the absence of fillers or thixotropic agents, mixtures of the two parts can be kept in a free-flowing liquid state at room temperature for hours, so that it is usually possible in the morning of a working day to obtain a supply of the resin composition sufficient for the entire working day by mixing the to manufacture both parts. One part (part A) is usually based on a polyglycidyl ether of a polyhydric phenol, is preferably at least 1.5 oxirane groups per average molecular weight and a viscosity of less than 30, 000 cP at 24 ⁰ O has. The second part (Part B) usually contains a mixture of

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(1) a carboxyl group-containing reaction product from castor oil and certain dicarboxylic anhydrides and (2) a low melting point Dicarboxylic anhydride in excess over the amount of anhydride required for complete carboxylation of the Rieinusöles is required. ■.

Dicarboxylic anhydrides which can be used to prepare the carboxy-containing reaction product of castor oil include maleic anhydride and dicarboxylic anhydrides having a melting point not higher than about 40 G, which are adducts of maleic anhydride with olefins. A suitable anhydride of this class is ethylenedomethylene tetrahydrophthalic anhydride, a light yellow, semi-viscous liquid with a viscosity of 138.4 cP at 25 G, which is commercially available under the name "Methyl Iladic Anhydride". Another suitable anhydride is the adduct to the lyre I s and K'r'ile insäur e.nnhydr id, - can be prepared daswi'e follows: 15 »6 kg of maleic anhydride are ge in a Iieaktionsgefäß. _; : -and take heated to 62.3 ⁰ G. In the G-efäii ^ slowly 28.8 are given kg My rc s, and .. "ale Ze: mpe temperature of 'Reaktionspartntr ν, imtoriialb -ird of C-5.6 3 held until the geea'ite myrcene added . ict -II aeh ended, ^ u ^ abe of the My-rcens wii'd the ^{Henktioiisgef:} iis - 2 hours at 93 ', heated 3 ⁰ C Ids is allowed to cool to soüami o5,6 G ⁰ ± 3e achieving this.. Tempo ratur v.'ira aar. Pressure inneriialc of the reaction vessel ■ slowly to'.JO - 30 mn Hg verriinä-art, v / anach äie ier.rer'a'tur to 148.9 ° G ^ est. . ^r ird .... Venn: ä? .s ^ e? a :: ite distillate ir. this

009831/1780 ^ - - * ■

■ SAO ■ -0.RfGlNAL.

Has been removed, the reaction ^{vessel is cooled to 79 »40} O, and the low-melting reaction product, the myrcene-maleic anhydride adduct, is drawn off into a storage container. Other useful anhydride adducts of maleic anhydride and olefins are the hexahydrophthalic anhydride (melting point 36 ⁰ C) and the alkenyl succinic anhydrides, such as the liquid Tetrapropeny! Anhydride, which can be prepared by reacting equimolar amounts of maleic anhydride and a Qlefinmaterials that tränieren mainly of the Te of Propylene is to be heated together.

The same anhydrides can be used for the above-mentioned constituent (2), ie for the anhydride which is used in excess over the amount required for complete carboxylation of the castor oil. The tetrapropeny / succinic anhydride is particularly useful for this purpose, since it provides classes of very low viscosity. Hexahydrophthalic anhydride is also a particularly good viscosity reducing agent. Maleic anhydride is less preferred for this purpose as it tends to volatilize and pose toxicity problems. It is generally used in amounts of at most one anhydride group of the calcium anhydride per hydroxyl group of the castor oil.

The carboxyl group-containing reaction product can in can be easily prepared by adding a mixture of equivalent amounts of castor oil and dicarboxylic acid an- hydride, i.e. a mixture in which for each anhydride group one

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Hydroxyl group of castor oil is present for several hours Heated at 121.1 C. The reaction is triggered by an esterification catalyst such as tin (.Il) octoate or tin (II) fluoride or a tertiary amine, greatly accelerated. At lower temperatures, the same product is produced with longer reaction times obtained, and even at normal room temperature, the carboxylation of castor oil is present after 2 months an esterification catalyst almost completely. Accordingly, part B of the resin compositions according to the invention can consist of Castor oil and the low-melting anhydride adduct without prior Implementation of these two substances are compiled, when an esterification catalyst is incorporated. Here will then esterify after the usual period of time required for packaging, storage, shipping and distribution is needed before the masses are used, usually be nearly complete. But even if this is not the jail, mixtures of the polyglycidyl ether provide and the partially carboxylated castor oil plus that Excess of molten anhydride hardened products, which practically did not differ from those products in which the castor oil had previously been completely converted can be. In fact, the invention Masses are brought onto the market in such a way that there is only unreacted castor oil in one part, while the other part contains both the polyglycidyl ether of the polyhydric phenol and the entire amount of the anhydride,

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as long as only one esterification catalyst is present to initiate an esterification reaction between the castor oil and the anhydride ensure when the two parts are mixed together will. However, this type of packaging is generally less preferred because of the lower shelf life, there is a tendency towards a conversion between the polyglycidyl ether and the anhydride. Furthermore, at least part of the anhydride is preferably incorporated into part B, the the castor oil or the carboxyl group-containing reaction product of the castor oil's contains in order to increase the volume of the two parts to make the same lighter dimension.

The novel haters of the invention should contain about 11/2 oxirane groups of the polyglycidyl ether for each carboxyl group contained in the castor oil reaction products and for each anhydride group of the unreacted anhydride. \ Tenn far more than 1 i / 2 oxirane groups account for each carboxyl and anhydride group, there is a considerable risk that not all !! close the polyglycidyl ether are reacted * - In this case, the cured product may be subject to an undesirable degradation when it exposed to adverse conditions. If there is less than one oxirane group for each carboxyl and anhydride group, the cured product is less "resistant to high temperatures, both in terms of electrical insulation properties and resistance to degradation. At current market prices, however, that is Polyglycidy1-

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. ether much more expensive than castor oil and low-melting anhydrides, so that for applications where it is The total number of carboxyl and anhydride groups, the number of oxirane groups, does not depend on the very best properties can exceed »

The amount of castor oil (if it is in the esterified state, see the amounts given to the amount of castor oil before the reaction with the anhydride) in the novel compositions of the invention should be within the approximate range of 40-110 parts by weight per 100 parts of the Polyglycidyl ethers of the polyhydric phenol lie. If less than about 40 parts, the cured product may have less toughness and flexibility than is desired; on the other hand, if it is well above 110 parts, the cured product tends to be somewhat weak and the high temperature electrical insulation properties that are the primary aim of the present invention, do not possess zvl .

Some or all of the castor oil can be replaced by liquid adducts of ricinoleic acid and polyhydric aliphatic alcohols, such as glycerol, dipropylene glycol, pentaerythritol and trimethanol or propane, " _o Such adducts are characterized by the following properties!

Molecular weight about 350-1100, hydroxyl number about 100-350
:! Functionality about 2-5
- Viscosity at 24 ⁰ G = 3000 - 4000 cP ₀

To simplify the terminology, the designation • Castor oil * - except in the examples - in a comprehensive and general sense used to include these ricinoleic acid adducts to include.

The pure oil should be purified and cannot be used non-hydrogenated or partially hydrogenated. However, the WlJS iodine number is preferably greater than 50. With iodine numbers above 50, the castor oil and its adducts are sufficiently free-flowing that the initial viscosity of the compositions according to the invention is well below 30,000 cP at 24 ^° C., while it is when using more highly hydrogenated castor oil preparations It can be difficult to stay below this viscosity value.

The novel compositions of the invention should contain at least about 20 more anhydride groups of the low-melting dicarboxylic acid anhydride adduct than is necessary for complete oxy lation of the castor oil. ^{In the} absence of such an excess of the low melting unreacted anhydride, the cured product tends to be somewhat poor and inferior for general electrical embedding purposes.

The compositions according to the invention preferably contain catalysts of the type used to accelerate the curing of acid cured epoxy resin compositions in such an amount that the two-part mass is within

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»Ο,

Is practically hardened for 16 hours at 150 ° C. To suitable catalysts include tertiary amines such as dimethylbenzylamine and its salts; Lewis acids, such as tin (rv) chloride or boron trifluoride, usually in the form of an amine complex; and metal soaps such as stannous octoate.

Particularly useful as polyglycidyl ethers are liquid condensation products of epichlorohydrin and bisphenol A. Typical of such condensation products is the commercial product "Epon 828", which has a Durrans softening point of about TO ⁰ C and an epoxy equivalent weight of about 190. Another class Useful liquid epoxy resins are the epoxidized novolaks, a typical example of which is Borden's "Epiphen 849", that of Borden with a viscosity at 25 ° O of 10,000-20,000 cP, an epoxy equivalent weight of 180-200 and the following structure was identified:

CH ₀ -CH-GH ₀ -O \ 2/2

-GH ₂ -GH-CH ₂

0-CH ₂ -CH-CH ₂

21

The diglycidyl ether of jiesorcin is also useful.

It has a lower viscosity in the compositions according to the invention and to give the cured product greater flexibility

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- ίο -

borrow - although a certain deterioration in toughness must be accepted - monoepoxides can be used in Amounts of up to about 20 wt .- ^ of the polyglycidyl ether incorporated will. However, the amount of these monoepoxides may only be so large that there is still a slight hardening to a tough, practically infusible, insoluble state is reached. Typical monoepoxides that can be used are dodecene oxide, octylene oxide, Dipentene monoxide, ^ C-pinene oxide, styrene oxide, phenylglycidyl ether, Vinyl cyclohexene monoxide and epoxidized long chain olefins, such as those with 16-18 carbon atoms.

Reaction product of Rieinus oil and maleic anhydride

This reaction product was prepared using £ 3 castor oil which had a WIJS iodine number of 86, a hydroxyl number of 154 (1 mol of hydroxyl groups per 365 g) and a viscosity of 660 cP at 25 ° C. The following approach was assumed:

Weight texle 7 / ^ 3-Rioinus oil 365 Maleic anhydride 98 Tin (II) octoate. 0.46

The castor oil and the tin (II) octoate v / ere mixed together and heated in a glass flask at 121.1 ⁰ C. The maleic anhydride was added with stirring while the mixture .wurde allowed to cool to 93 '3 ° G, after which the entire mass under frequent stirring for 2 hours at 121.1 ⁰ O heated to boiling wur-

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de. The reaction product was a clear liquid which had a viscosity of 4300 cP ^{at 24 0 G.} It had a saponification equivalent weight of 147, from which it could be calculated that there were 1 mole of ester groups per 225 g. This means that all of the hydroxyl groups were esterified with the maleic anhydride. The non-aqueous titration gave an acid equivalent of 2.35 meq / g, while the aqueous titration gave an acid equivalent of 2.52 meq / g. The difference between the fourth obtained in the aqueous titration and the value obtained in the non-aqueous titration means that the product contained some free maleic anhydride. This was also evident from the results of the infrared analysis. The product was contractual with "Epon 828" polyglycidyl ether at room temperature in all proportions. '. .

Reaction product of ricinup oil and ilexahydrophthalic anhydride

Parts by weight

// 3-castor oil '365 hexahyirophthalic anhydride 154 2inii (ll) octoate O ₅ 5

The Hexahydrophtalsäureanliydrid was tei 65> 6 ° 3 melted and the Sinri (II) octoate mixed with "the Hicinusölund in a glass flask. The mass was heated to 1'21,1 ⁰ C. 'and Freq strength Eüiiren 2 hours at this The reaction product had a viscosity of 55,000 cP at 2Δ. C to _o ·

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The aqueous titration gave an acid equivalent of 2.15

Examples 1 - 3

The reaction product of castor oil and maleic anhydride described above was mixed in various proportions with tetrapropeny / succinic anhydride and tris- (2,4,6-dimethylaminomethyl) phenol to form stable mixtures, which were then mixed with a liquid polyglycidyl ether of bisphenol A ("Bpon 828") were mixed to form mixtures of the following composition:

1 '2 3

"Epon 828" 100 100 100 Carboxylated castor oil 80 80 80 Tetrapropeny! Succinic acid
anhydride 90 82 70 Tris (2,4,6-dimethylamino-
methyl) phenol 1.55 1.5 1.2!

The ratio of the oxirane groups of the polyglycidyl ether to the sum of the carboxyl groups of the castor oil-maleic anhydride reaction product and the anhydride groups of the tetrapropenyl succinic anhydride were as follows: Example 1 = 1.02; Example 2 = 1.09; Example 3 = 1.20.

The initial viscosities of these materials were in the range of 4000-5000 cP at 24 C. Castings of these compositions gelled within 20 minutes at 120 ⁰ C and exhibited after 6 hours of curing at this temperature for the following properties. The water absorption test runs were carried out by

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Immersion of castings carried out the dimensions of 76.2mm by 25.4mm by 3.175mm. The heat resistance was determined by taking castings with dimensions of 50.8 mm χ 50.8 mm 12.7 mm placed in an air-circulating oven at 155 ° C became. 1 2 3

Hardness, Shore D 72 70 65

Water absorption:
Weight gain after 1 week of immersion at room temperature

Weight gain after 1 week Immersion at 100 ° 0

Shore D hardness after immersion at 10O ⁰ O

Heat resistance: weight loss after 1 week in the oven at T55 ° G

Shore D hardness after the test

Mechanical shock resistance

(U.S. Mil.spec. M11-I-I-16923D) Specimen resistance ball size:

95.25mm 95.25mm 95.25

0.4 f> 0.5 ■ f> 0.4 4.7 $ ' 2.2 io 2.5 50 30th 30 ■ 1.4 i ° 0.8 io 0.7 80 80 82

Dielectric dissipation factor
at 109 volts and 100 Hz
at 25 ° ^α ο, 02 0.03 0.02 105 °,; 0 ■ ο, 16 0.04 Q, 02 "", 155 ⁰ O + 1.51 0.37 180 ⁰ O + 0.45 Dielectric constant at
■ 109 volts and 100 Hz
at 23 ° 0
1050 σ
155 ° C
180 ° 0 3,
5,
+ 3
O 3.5
4.9
11.9
+ 3.5
5.0
4.7
.4.5 00 9831 / 1780 BATH ORIGINAL

Specific resistance at
500 volts direct current
(ohm / cm), 2,3x1O ^U 3 , 9x10 ^U 2.2x10 at 23 ° G 4,3X1O ¹⁰ 9 , 9X10 ¹⁰ 2.5x10 105 ° G 4.4x10 ⁹ 2 , 5x1O ⁹ 1.9x10 155 ° G 3.7x1O ⁹ 2 , 1x10 ⁹ 1.4x10 130 ° G

V / ert was outside the scale of the meter used.

The above data show that the cured products of Example 3 are characterized by exceptionally good toughness, degradation resistance and electrical insulating properties and represent a very significant advance in these properties when compared to the previously known flexible type resin products. The products of Examples 1 and 2 are also better than the known products, but do not quite reach the ^T, the product of Example 7erte third

Example 4

The eicinus oil-maleic anhydride reaction product was still used to make the following recipe:

Parts by weight

"Epon 828"

Eic inus oil-times into the acid anhydride reaction product

Hexahydrophthalic anhydride Powdered talc dimethylbenzylamine

100

90 43 155 1.16

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Da3 ratio of the oxirane groups to the sum of the Oar-; boxyl groups of the Pacinusöl reaction product and the unreacted Anhydride groups in the bulk was about 1.09.

Castings made from this mass gelled within 15-20 Minutes at 120 C. After curing for 16 hours at this temperature the following properties were measured - with the same measurement as in Examples 1 to 3: Hardness (Shore D) 75

Water absorption

Weight gain xiach

1 week at room temperature O, 29 % ■ ■ 18 Io 4.63 3.7 x 10 ¹³ Weight gain after
1 week at 10O ⁰ G 6, 4- * 6.56 2, Ox1O ¹¹ Shore D hardness after trial
at 10O ⁰ O 57 5.39 3.6 10 ^ΐ0 . Heat resistance: 55 mm 5.30 • 2.4- x 10 ¹⁰ Weight loss after T week
in the oven at 155 ⁰ O O, . Dielectric Dielectric Specific
Loss factor constant - resistance Barcol-ilLi-rte after trying 24 at 23 ⁰ C 0.036 Mechanical shock resistance: 105 C ⁰ 0.059 82, 155 ⁰ O 0.234 130 ⁰ C 0.301 Specimen resistance ball size

00 9 8 3Λ / 1 7 8 0 BAD

- 16 - ■

Example 5 Weight parts

"Upon 828" 100

Ricinus b'1-hexahydrophthalic acid anhydride

Reaction product 90

Tetrapropenyl succinic anhydride 72

Tris (2,4,6-dimethylaminomethyl) -

phenol 1.3

The ratio of the oxirane groups of the "Epon 828" polyglyoidyl ether to the sum of the carboxyl groups of the castor oil reaction product and the anhydride groups of the tetrapropenylsuccinic anhydride was about 1.20. The initial viscosity of the mass at 24 ^° C. was 8000 cP.

On heating to 120 ⁰ O mass gelled in about 15 minutes and was after 2 hours at dieeer! Temperature cured to a tough casting, which had a Shore D hardness of 66 hti room temperature. The casting, which had dimensions of 50.8 mm × 50.8 mm × 12.7 mm, showed good impact resistance because it did not braeh when repeatedly thrown onto the floor.

Example 6

70 parts of hexahydrophthalic anhydride were melted at 65 "6 ⁰ O and with 100 hone" Epon 828 "-Polyglycidylätaer mixed. Then 63 parts of 3-castor oil and 1.2 parts of tris-2,4,6- (dimethylaminomethyl) phenol were mixed in, a thick, incompatible, but free-flowing liquid masa

■ Ϊ - 1 · I

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Γ · (viscosity at 24 ⁰ O less than 30,000) was obtained, which became clear when heated to 67 ° © and had a very low viscosity,

This composition gelled in 15 minutes "at 120 ⁰ C and after 2 hours was a clear, hard, tough G-ießling (50.8 mm 50.8 mm χ χ 12.7 mm) cured at 24 ⁰ C of a Shore D hardness of 72 was obtained. the casting was not broken when he wurd§ hard thrown against the floor> the Iris 2.4 * 6- (dimethylaniijiome.thyl) -phfnol was ^r here both as Veresterungskataly 3 »tor as also used to accelerate the hardening with the poly- ^ lycidyl ether « -. *

Example ^ ■ ": '., _F

To 170 parts of the same JU ^ ydrid-Poiygiycidyläther-Mixture 60 leile "Polyoiii 55" were given. This is an adduct of ricinoleic acid and a polyvalent aliphatic alcohol, since it has an approximate functionality γόη 2.2, a hydroxyl number of 254, a specific density of 969 at 25 ⁰ and a yis ity of 3 ^ 0 at 25 ⁰ O. To this Misohung 1.15 ropes 5ris-2,4,6 (dimethylaminomethyl) phenol given "Dit mass was clear and wiea a Yiskosität of 1150 cps at 24 ⁰ C.

When heated to 120 ⁰ G, the mass gelled in 15-20 minutes

utes undi was after 1 hour to a clear, hard, tough

Casting) [508 mm 50.8 mm 12 * 7 mm) hardened, which showed a Shore D hardness of 50 ^{at 24 0 O.} The hardened product

SAD ORIGINAL

was tested according to the test method US.Mil.Spec.Mil-I-16923D (der However, the casting had different dimensions than there) tested for mechanical impact resistance, the test specimen the 95.25 mm bullet resisted. This toughness value shows that all constituents of the composition took part in the hardening reaction to have.

In the thermosetting compositions of the invention can optionally a wide variety of pigments, thixotropic agents or fillers (grains or fibers) are incorporated. E.g. have mica, talc. Calcium carbonate and silica

■ *

Proven to be useful as hardened products that simplify large percentage of these materials contained in powder form, excellent strength, toughness and electrical properties Showed insulating properties.

Since compositions of the invention 'are put on the market to achieve greater consistency in two parts, it is usually desirable, they are different to

color so that it can easily be determined whether a full; constant mixing has been achieved. . ■

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Claims (1)

* Claims 1,! »Solvent-free, thermosetting, electrically insulating Resin compound, which in the absence of a filler is initially a free-flowing liquid at room temperature, with moderate heating, however, to a tough, flexible, heat-resistant State hardens, the mass essentially consisting of a mixture of. (A) a Polyglyeidyläther a polyhydric phenol having a viscosity of wenige'r 30 000 eps at 24 ⁰ C and at least 1.5 oxirane groups per average molecular weight. ' (B) a homogeneous grism mix of ' (1) Castor oil with a jod number of at least 50, where the amount of castor oil 40-100 parts by weight each 100! Parts of the polyglycidyl ether and ' (2) Picarbönsäureanhydriden, namely maleic anhydride ⁰ or maleic anhydride4-01efin adducts, their Melting point is not above 40 ⁰ O;, characterized in that the mass 1.1 to 1.5 oxirane groups of the polyglyeidyl ether for each by reaction between. The castor oil and the anhydride contain carboxyl group generated and for each anhydride group unreacted anhydride and at least 20% more anhydride groups than are necessary to create an anhydride group for each syäi-pxyl group originally present in the castor oil. BADORlG-IiNLAL jpO9831 / 1TtO _. . 1570061 - 20 - 2. Thermosetting resin composition according to claim 1, characterized in that that the castor oil with a, feil dee dicarboxylic acid anhydride is anticipated. 3 » Thermosetting resin composition according to claim 1, characterized in that the castor oil is a liquid. Adduct of ricinoleic acid and a polyhydric aliphatic alcohol is " 4. Thermosetting haremasse according to claim 1, 2 or 5, characterized in that the dicarboxylic acid is maleic anhydride is" 5. Thermosetting resin composition according to claim 1, 2 or 3j, characterized in that the dicarboxylic acid is hexahydropatalsic anhydride. 6. Thermosetting resin composition according to claim 1, 2 or 3 »thereby characterized in that the dicarboxylic acid is an Aikenylfcem'-stinic anhydride is" 7. Thermosetting resin composition according to claim 1, 2 or 3t characterized «that the dearboxylic acid is myrcene maleic anhydride» # 8. Thermosetting resin composition according to claim 1, 2 or 5 » characterized in that the dicarboxylic acid is methylendoeethjflentetrahydrophthalic anhydride. 9 · Solvent-free, thermosetting electriolite ^ Rende Harzmasee in the absence ron tulle anfftnglicJa ■. ; 009831/1780 a free-flowing liquid at room temperature is j but with moderate heating, hardens to a tough, flexible, heat-resistant electrical insulation, the Hasse consisting of a mixture of (A) a polyglycidyl ether of a polyhydric phenol with. a viscosity of less than 30,000 cps at 24 ⁰ G and at least 1.5 Qxiran groups "per average molecular weight
($ 3) a homogeneous; Varnish off anyway. - . ■ '■ (*} Bioinusil ^ mii one <Γ ^? Ιοίϊί.γοΊΐ aiftdöß-feöns | pO, where- ■ fcsöt diet Höngt the Si ^ lauecltöi 40 * IiO Öewiöfttsteile | e tOO.! Peile des Polyglyoidyiätiiörs is, ■ ■ ■■. ναιά '■. ■ "- ■ - ■■ .. - - (b) a carbonic acid anhydride, namely maleic acid ^ * anhydride or MaleingMureanhydrid-Olefin adducts, which have a melting point not greater than .4-O ⁰ O » (2) an additional Anhydridaddukt of · time one is äurean ^ anhydride and olefin, the Äddukt a melting point not higher than 4O ⁰ C has "characterized labeled in ** is characterized in that the composition has a ratio of-Oxirangrüp * - pen of Pölyglycidyläthers to the entire Öarboxyl- ^ groups of the carboxy oil-containing reaction product (1) pl ^ s unreacted anhydride groups within the - ■ I - - ■■ ■■ ■ ■ ' range from 1j1 : 1 to 1 ^ 5 ί 1 has> and at most one anhydride group of sharkic anhydride per original .- '■ ■' ■,.: -: ■ - "- ■. / ■" ■■ ■ .- ^: .-. '- .- .. · ■ ■■■, "SAD ORJGiNAt 1510961 originally present in the castor oil hydroxyl group, and the mass at least 20 $ more anhydride groups than necessary to create an anhydride group for each hydroxyl group originally present in the castor oil are. 10. solution free, thermosetting electrical insulating resin composition for hours in the absence of! Filler can be maintained as a free flowing liquid of less than 30 "ÖOO gs" in Raumtempsratur '& $ βτ * with moderate heating to a tough, flexible, wärmefesteij elökiä ^ isclien insulating compound hardens, characterized in that the compound is a chemically, (A) a polyglycidyl ether of bisphenol A with a viscosity of less than 30,000 cps at 24 ⁰ O and at least 1.5 oxirane groups per average molecular weight. and (B) a homogeneous mixture (1) the carboxyl-containing reaction product of (a) Grlyceryltririeinoleate castor oil having an iodine number: of at least 50, the amount of the Rieinusöl; 40 - 110 (parts per 100 parts of polylglyeiyl ether, and '* ■ (b) a dicarboxylic acid anhydride, namely Maleinsäurer · anhydride or maleic anhydride-olefin Adiukten that aufwei- a melting point of not more than 40 0. _^: i sen, and - 009831/1780 ■ '.-; ■ is; ff-ι ⁵ ■; ■ --- ■; ■■. ' - ■■. - ■ "■" ■ - _x · 1 , '- "■.;V' - 23 -.- .;. ■ (2) additional Anhydridaddukt of maleic anhydride and olefin, the "inen melting point does not have about 4O ⁰ C, wherein in the mass a: ratio of Öxirangruppen of Bolyglyciäylathe rs to total carboxy groups of the carboxyIhaltigen Eeaktionsproduktes (1) plus niehtumge" translated Etihydride groups are within the range 1.1 i 1 to 1.5 ϊ 1 and the composition contains enough anhydride to contain at least 1.2 anhydride groups, but not more than one maleic anhydride group for 3? each hydroxyl group ° in the castor oil before TJM, - "reduction to provide dea with anhydride", dd Solvent-free, thermosetting, electrically insulating Harsraass®, the Mn absence of filler for hours as a; free-flowing "liquid of less than OÖO cps b @ i room temperature can be maintained, but with moderate heating to a tough & n ₉ flexible, heat-resistant elelctrisclien IsölieEaasse hardens., * iaduröh gekesmseieh- ; ' _r that the hatred from a 'mixed day of .of Biaphenol A with a VisTcosi- ity of "less than 30,000 cps at 24- ⁰ C toad at least t, "5 Öxl3rang £ uppen; each" Surbliselanittsmolekulargewicht _s (B) of fine homogeneous mixture. " (1) Aeia resistance product of equivalent amounts of (a) ^ lyceryltriiiicinoleate ^ aieinusöl with egg «death number νοίϊ at least 5Ö »where the amount of the egg sinSle» ..- '■' ■ .. ■■ "'■'; .. ■■ ■ SADORiGJNAf 0098317178 0 - 24 -. "40-110 parts by weight per 100 parts of the polyglycidyl ether" is, and
Maleic anhydride, and
(2) anhydride adduct of maleic anhydride and olefin, the has a melting point of not more than 40 0, and the mass is a ratio of oxirane groups of the polyglycidyl ether to the total carboxyl groups of the esterification product (1) plus anhydride groups of the anhydride adduct (2) is within the range 1.1: 1 to 1.5 ϊ 1 and to each Carboxyl group of the carboxylated reaction product at least 0.2 anhydride groups of the anhydride adduct (2). 12. Process for the production of a solvent-free, thermosetting electrically insulating resin composition which, in the absence of filler, is initially a free-flowing liquid is at room temperature, but hardens to a tough, pliable, heat-resistant state on moderate heating, thereby characterized in that one is a mixture of (A) a polyglycidyl ether of a polyhydric phenol with a viscosity of less than 30,000 cps at 24 G and at least 1.5 oxirane groups per average molecular weight, (B) Castor oil with an iodine number of at least 50, the amount of castor oil being 40-110 parts by weight per 100 parts of the polyglycidyl ether is, and (G) Dicarboxylic acid anhydrides, namely maleic anhydride or Adducts into the acidic acid and olefin, the one Have a melting point of not more than 40 C, said ingredients being used in such amounts that a ratio of the oxirane groups of the polyglycidyl ether to the anhydride groups of the dicarboxylic anhydride within of the range from 1.1 s 1 to 1.5 s: 1, and where at least 1.2 anhydride groups for each hydroxyl group of the castor oil come. 13. "The method according to claim 12, characterized in that that the castor oil is almost completely esterified with the anhydride before it is mixed with the polyglycidyl ether. 14. Solid, impact-resistant, hardened resin product obtained according to the composition in claim 1. - M 1712
Dr.Pa/Ti OBIQlHAL 'ifilü / lfti.