FR2503169A1 - REACTIVE ACCELERATORS FOR EPOXY RESIN SYSTEMS CURED BY ANHYDRIDES - Google Patents

Abstract

REACTIVE ACCELERATORS FOR ANHYDRIDE-CURED EPOXIDIC RESIN SYSTEMS. THESE ACCELERATORS CONSIST OF BIS-MALEIMIDES OF THE GENERAL FORMULA: (CF DRAWING IN BOPI) IN WHICH R REPRESENTS: (CF DRAWING IN BOPI) N0 A 10, R AND R, IDENTICAL OR DIFFERENT, EACH REPRESENTS A DIVALENT HYDROCARBON RADICAL.

Description

The invention relates to reactive accelerators

  for epoxy resin systems hardened by anhy-

  these accelerators are characterized by fast curing, avoiding the formation of odorants and substances that affect

dielectric properties.

  These accelerated epoxy resin systems can

  can be used advantageously as low-pressure molding materials as well as as adhesive resins, casting resins and laminating resins, especially

  in the fields of electrical engineering / electronics.

  When epoxy resins are cured with, for example, amines, anhydrides or catalysts of

  polymerization, no volatile products are formed.

  That is why this class of substances is used with advantage in many industrial branches as adhesive resins, resins for

  flow, and resins to be laminated. Epoxy resin systems

  Non-accelerated dic anhydride require relatively long reaction times of several hours at elevated temperatures and above 150 ° C. We know

  already various accelerating systems that allow

  ter the reaction time. Among the usual accelerators for epoxy resin-anhydride systems, mention may be made, for example, of polyalcohols such as glycol or glycerol, tertiary amines such as dimethylbenzylamine,

  triethanolamine or 2,4,6-tris- (N, Nt-diaminomethyl)

  phenol. Among the accelerators developed more recently for the epoxy resin-anhydride systems, mention may be made, for example, of phenyl tin trichloride (DE Patent No. 1,495,306), which allows a hardening of dialkyl pyridines between 20 and C (US Pat. -United

  No. 3,440,216), polymercaptans bearing

  droxy (DE patent 2,400,948) and a combination

  chromium tricarboxylate and tertiary amines (

  BE no 779/557). In addition, phosphonium halides (US Pat. No. 3,547,885),

  reaction of melamine and dicarboxylic acids (

  No. 1 645 206), titanium, zirconium and cerium salts of aliphatic carboxylic acids (US Pat. No. 3,692,715) and tetraphenyl tetraphenylborate.

  Phosphoniue (US Patent No. 3,597,411).

  These systems, however, have one disadvantage: they are not incorporated, at least not completely, in

  the hardened molding material, and the result is a reduction in

  dielectric, thermal, optical and / or mechanical properties. Metallic or halogenated compounds

  contained in some accelerators also have an ef-

  negative effect, in particular on the dielectric properties of

  Queo. There is also an interesting possibility of accelerating the epoxy resin-hardener mixtures by means of synergistic mixtures of resole resins.

  cresolics and aromatic amines (DD No. 129,563).

  Another way to accelerate the hardening of epoxy resins by triggering the polymerization of epoxy resins using complex compounds of

  Br3 has the same disadvantages.

  In this respect, the following works may be consulted:

  after Jahn s Epoxidharze, pages 51 and following, VEB Deutscher Verlag far Grundstoffindustrie, Leipzig 1969; Paquin s Epoxidverbindungen und Epoxidharze, pp. 470 et seq., Springer-Verlag, Berlin-Gottingen Heidelberg 1958; Ludeck s Handbuch der Kleb-, Giess- und Laminiertechnik,

  pages 57 and following, VEB Deutscher Verlag fir Grundstoff-

industry, Leipzig 1979.

  In the DD 1314111 patent, a method is described.

  for preparing a hardened epoxy resin composition

  fast curing for injection molding, based

  of a liquid epoxy resin, methyl

  hexahydrophthalic acid and 2,4,6-tris (dimethylaminomethyl)

phenol which serves as accelerator.

  The main disadvantage of this process is that the accelerator is not fully incorporated

in the hardened system.

  Further information on accelerations

  for the epoxy-anhydride resin systems in the publications cited above as well as in Ullmann,

  Enzyklopadie der techn. Chemie, volume 8, page 434 and following

  vantes, Verlag Urban & Schwarzenberg, Munich-Berlin, 1957; Vieveg s Kunststoff-Handbuch, volume 11, Polyacetale, Epoxidharze ... Carl Hauser Verlag, Munich 1971, B. Dobinson's Report on the Progress of Applied Chemistry

59 (1974) pp. 78-87.

  We also know molding materials that we

  form by hardening epoxy resins with bisphenols

  1 maldimides and polyamines. Such products are described in DE No. 107,300, DE No. 2,559,417, US Patent No. 3,978,152, and DE Nos. 2,230,904;

2,026,423 and 2,354,654.

  Heat-curable resinous compositions are still known (DE Patent Application No. 2,927,995) which contain the reaction mixture formed by melt reaction of a diamine with an acid anhydride.

  carboxylic acid, and an epoxy compound.

  These products and methods of the prior art differ from the present invention in that they use

  another epoxy resin-hardener system.

  DE Patent No. 2,446,697 describes the addition of

  from monoallyl maleate to the hardening of epoxy resins

  diques and anhydrides of polycarboxylic acids.

  In DE No. 2,101,929 a process is described.

  for preparing thermosetting compositions containing

  epoxy resin-anhydride mixtures of carboxylic acids and bis-maldimides (BMI). In this process, BMI is used in proportions of 40 to 250% by weight of the epoxy resin. In the patent application DE

  published under No. 2 123 638, compositions of

  in which the proportion of bis-maleimides T OTUifupu otnuTxOj op sopTTplvTm-sTq sep opTpúlquu-enbTpúxodp aUTZpj sneqossu ç op UOT4vjpTpOOwTl inod uUOsTTTn uuoS UOTe.SUT.T l sueupW -.osuoo SnTospa 4uo "snssep-To spoodrs * emqTqoid sel * se0dw -To uoT4dTiosop VI op oanqoet ut 4 UOI4 -TuZuiddu uoTqUAUTiT Op so2u4UBuVA S0 s9nq aSO.na, "* os.qmltod nuvospa and sup oTvoq uoOTuwjod.zoouT sun uu.xnssu OC apTidoiddu" jTqOupi sodnoL * op uOptesood Tnb oplpquu -enbTpLxodq eUT * T ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo ..... sop uoTsuJOTTPmW sun j edmos emou us XTUOA.ud ó; e To-rp le.qs ST suump xnSU.zpTpooUwT oP eqTldmoo uoT @ a4z ,, uT sun zesu.nei T ** TA UOTSUOAUTTI UoT $ PPTTppaod 5ud TU uo3usTazpTTod. [d TU eesjqTmoUd sSeqT: a soil of the south and south of the country where speTTTFln can be found on the ground. uoeTnlos sop read; ueaupuoj qusTupAuOounTF * 3-4omoeToxp op sfnoIagTpIoo qumTllTonTqaq * sp * OSTTTn uo sou 'pum * -o OoAy uoTsueAuT eolueospd ur i eonoTSpuu onbTuqoo sun suits or T ouop quenT4suoo o oTLTTu smdnouoS * op quoqod Tnb OBNB -TP <xodf sgoduoo sep T pqTMTTI 4uos eohsuuTpm seo '* $ Jos nol * sonbTTlxoqauo sepTsWp sepTipLquu sop SebTpLxsdp sepTep Sep sepT. TpTam-sTq sop * To $ * T q! IutuueT4uoo Tub (TIZ 9Z Z or enos OSTiqnd 3a qSAosqop opusop) senbTp 01 -Ixodp sOUTspI op eoDuuT. * Op oz1no us uTuoo uf * * onbTLTxoqzwo pTovaP apTiplquv-onbTpXzodp ouTega soeuwlpm op 4SoueosTo -znp not 4uomeoaodwoo sT years INH op suoTnouorpu 4Tçqe * d op op UOT4OeaT gad elted gouo uo to $ quoTTqnd gseo uam eanbTlXoqzao sepTou1p * * opTipliquu sop ow sonbTpXxodq couTgi sop puos osnouTagi uoTqTsodwoo sT op 4Uen4TqoUOo gsoenu sol * Taulo0 euTYgi uT op gpTod us saT4sd 0O1 nod spTod us oeTqa "d 09 j OC op oTjuA

69Lú0ZS

Formula 1

CH - CO \ / CO - CH

he -, N \ N he

CH -C R CO CO - CH

in which R represents

CO - CH CH -

- R '- [N / 2 "2

CI t

CO - CH - NH-R "-NII-CH -

CO

N-R'C_

"CO n has 0 ... 10

  * 0 R 'and R "may be the same or different.

  The bis-maleimides in which Rt and Ru have

  the meaning hereinafter is particularly suitable for

C6H4 - C614

C614 - H2-C6H4

C6H4-0-C6H4

c6M4-S02-C6o4

C6H4, C3H6, C6H4

  C6X4-CH (c6115) OC6 4 C6H4-C6HlowC6H4

C6R4-CO-C6H4

m-C6H4

P-C6H4

  C2H4 C6Hlo C6H10-CH2-C6H10 CH2-C6H10-C6Ho10-CH2

1,3- (CH3) 2-C6H2

4,41-BIA- (maleimido) biphenylene

4,4-bis- (maleimido) -diphenyl-

methane

4,4t-bis (maleimido) oxide -

diphenyl ether

4,4t-bis- (maldimido) -diphényl-

sulfone

4,4'-bis- (maléimidopinyl) -2,2

propane

  4,4'-bis (maleimidophenyl) -phenyl-

methane

4,4t-bis (maleimidophenyl) -1,4

  cyclohexane 4,4t-bis- (maleimido) -benzophenone 1,3-bis (maleimido) -benzene 1,4-bis- (Maleimido) -benszen 1,2-bis (maleimido) -1-thane 1.6-bis (maldimido) -hexane

4,4'-bis- (maleimido) -dicyclo-

hexylméthane

bis- (maleimido-4,4'-methylcyclohexyl

  hexyl) 2,4-bis (maleimido) -m-xylene 1,4- (CH3) 2-C6B2 2,5-bis (maleimido) p-xylene

  C18H4-C2N2 (C6H5) -c6H3720 4,4'-bia- (3-phenyl) -6-oxide

  maleimido-quinoxaline-2-yl). These known bis-maleimides are prepared in the soil by reacting the corresponding diamines with the quantities

  double molar quantities of maleic anhydride in

  such as chloroform-divethylformamide blends,

  the reaction giving a amidocarboxylic acid quon con-

  in the corresponding imidec, using anhydridol

  acetic acid (US Patent No. 3,018,290 and GB Patent No.

1,137,592).

  Also available are: Macromolecular Syntheses, Volume 6, James E. Mulvaney, Editor, page 92, J.V. Crivello, John Viley & Sons,

  New York, London, Sydney, Toronto, 1977.

  Oligomaleimides which also exert

  catalytic reaction on epoxy resin-anhy-

  are prepared in a manner known per se (Europ.Poly-

  14 (1978) 129 pages 985-990) by reacting diamines with bis-maleimides at a molar ratio of less than 1: 1.25, at a temperature of about 100C in a polar solvent. When the reaction is complete, the compounds are isolated by precipitation in methanol,

  filtration and extraction with methanol.

  The bis-maleimides of general formula 1 in the

  n is greater than 0 are usually prepared by reacting an excess of bis-maleimides for which

  n = O with diamines in m-cresol in the presence of

  of acetic acid at a temperature of 100 to 160 C.

  Additions of bis-maleimides of about 1 to% cause a strong acceleration of the curing reaction of the low molecular weight epoxy resins

  or high molecular weight polyphenols, Novo

  lakes, triazines, polyols, siloxanes, aliphatic and cycloaliphatic olefin oxides and amines with aromatic, alicyclic, double bond and / or halogen, and mono- or poly-functional anhydrides. It is remarkable in this respect that

  using bis-maleimides, it is possible to achieve a

  combination of average shelf life before use

  with a short cure time.

  Good results are obtained with the following anhydrides: anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride phthalic anhydride tetrahydrophthalic hexahydrophthalic endomethylene-titrahydrophthalic methylendomethylene tetrahydrophthalic hexachloroendomethylethylene tetrahydrophthalic tetrachlorophthalic trimellitic maleic succinic dianhydride pyromellitic dianhydride bensophenone acid tetracarboxylic

  dianhydride of cyclopentane-titracarboxylic acid.

  The bis-maleimides function as reactive accelerators which are fully incorporated in the molding material by a complex reaction mechanism. It results

  high vacuum stability and the absence of odo-

  even under extreme conditions and for

  extended periods. Due to the presence of slate groups

  heat accelerators, these accelerators contribute to the

  thermal properties and oxidation properties

heat.

  Addition of the bis-maleimides to the epoxy resin-anhydride system is carried out as follows: The hardener is added in calculated proportions to the mixture of the accelerator and the epoxy resin and the mixture is melted. In this form, it can be used as an adhesive resin, a casting resin and a laminating resin. The hardening is preferably carried out in two stages of operation.

8 2503169

  a) Hardening Up to dimensional stability,

  b) demolding and hardening of the second stage.

  In die-casting or injection molding or pressure injection molding, the melting is carried out in the machine at

  at 285 ° C and hardening up to the dimensional stability

  (first stage) in the tool at a temperature of approximately 100 to 285 C depending on the system used in the

particular case.

  The hardening of the second stage (final hardening) can be carried out after removing the object from

  the tool at a temperature of 120 to 300 ° C.

  By varying the proportion of accelerators

  according to the invention, the hardening time can be shortened.

  in the tool and to achieve an optimal global technology for the work of the molding material. The adjustment to

  optimum values of the durations of use and hardening

  This leads to a considerable saving of energy and an increase in productivity. A 2% addition of 1,3-bis- (maleimido) -benzene makes it possible to reduce the duration

  hardening of a mixture of diane-epoxy resin-anhy-

  at a level of about 50% of that of the non-accelerated system. When using weighted bis-maleimides

  higher molecular weight eg 4,4'-bis-

  5-phenyl-6 (7) maleimido-quinoxaline-2-yl-diphenyl, leaching

  acceleration iron is weaker; but these compounds

  use higher proportions of accelerations

  and thus to improve properties of the molding material such as heat stability, heat oxidation stability, dielectric behavior and high temperature vacuum stability. In addition,

  using such compounds, the viscosity

  melts in a favorable direction for the use of

  lisation. An addition of 5% of the bis-maleimide mentioned above to a resin-diane-epoxy-anhydride mixture leads to a decrease in the hardening time.

  about 50%. In cases where we would like

  In addition, it is possible to use auxiliary catalysts, for example tertiary amines, Lewis acids, polyalcohols, chromium, cerium, titanium, zirconium, carboxylic acid salts and / or

polymercaptan derivatives.

  The following examples illustrate but not limit the invention; in these examples, the indications of parts and% are by weight unless otherwise stated

opposite.

Example 1

  For curing a system consisting of 100 parts of a low molecular weight epoxy resin,

  equivalent of epoxide 190, and 70 parts of phthalic anhydride

  that, it takes 118 mun 130 C to reach the state B. In

  adding 10 parts of 4,4'-bis- (3-phenyl-6-maleate) oxide

  imido-quinoxaline-2-yl) -diphenyl to this system, the duration

  needed to reach state B drops to 52 min at 130C.

Example 2

  For curing a system consisting of 100 parts of a low molecular weight epoxy resin,

  equivalent of 190 epoxide, and 70 parts of titanium dioxide

  hydrophilic, it takes 127 minutes at 130 ° C to reach

  state B. The addition of 10 parts of oxide of 4,41-bie

  (3-phenyl-6-maleimido-quinoxaline-2-yl) -diphenyl to this system lowers the time needed to reach state B to 57 minutes at 130 ° C.

Example 3

  To cure a system consisting of 100 parts of a low molecular weight epoxy resin, equivalent

  190 parts and 75 parts of hexahydrophthalic anhydride

  that, it takes 226 mn to 130 C to reach the state B. In

  adding 10 parts of 4,4'-bis- (3-phenyl-6-maleate) oxide

  imido-quinoxaline-2-yl) -diphenyl to this system is lowered to 117 min at 1300C the time required to achieve the state B.

Example 4

  To harden a system consisting of 100 parts

  an epoxy resin of molecular weight mie-yeu, equi-

  350 epoxide and 30 parts of phthalic anhydride are

  that it takes 38 minutes at 130sC to reach state B.

  adding 10 parts of 4, 4'-bis (3-phenyl) -aluminum oxide

  imido-quilnoxaline-2-yl) -diphenyl to this system, it is lowered

  At 19 minutes at 130 ° C the time required to reach

tat B.

Example 5

  To harden a system that consists of 100 parts

  of an average molecular weight epoxy resin, equi-

  350 epoxide, and 30 parts of tetrahydrofuran anhydride are

  phthalic, it takes 39 minutes at 1300C to reach state B.

  By adding 10 parts of 4,4'-bis (3-phenyl) -6-oxide

  Maleimido-quinoxaline-2-yl) -diphenyl This system reduces the time needed to reach state B to 21 minutes at 130.degree.

Example 6

  To harden a system that consists of 100 parts

  of an epoxidic resin of average molecular weight, equi-

  350 parts of epoxide and 35 parts of hexahydroxide anhydride

  phthalic, it takes 53 minutes to L30C to reach state B.

  By adding 10 parts of 4,4 "-bls- (3-phenyl-male)

  This system reduces the amount of

  33 minutes to 130OC the time needed to reach state B.

Example 7

  To cure a system consisting of 100 parts of an epoxy equivalent epoxy resin epoxy resin and 70 parts of phthalic anhydride, it takes 69 minutes at 130 ° C to reach the B state.

  of 4,4'-bis (3-phenyl-6-maleimido-quinoxaline-2-oxide

  yl) -diphenyl to this system, it reduces to 32 minutes at 1300C the time required to reach the state B.

Example 8

  To cure a system consisting of 100 parts of a novolac epoxy resin, epoxide equivalent 180, and 75 parts of tetrahydrophthalic acid, it takes 72 minutes 11 to 130 ° C. to reach the state B. By adding 10 parts

  of 4,4'-bis (3-phenyl-6-maleimido-quinoxaline-2-oxide

  yl) -diphenyl to this system is lowered to 40 minutes at 1300C the time required to achieve the state B. Example 9 To harden a system which consists of 100 parts of a epoxy resin novolac epoxy equivalent, and 80 parts of hexahydrophthalic anhydride, it takes 228 mn to 130eC to reach the state B. By adding

  10 parts of 4,4'-bis- (3-phenyl-6-maleimido-quinoline) oxide

  xaline-2-yl) -diphenyl to this system, the time necessary to reach the state B is lowered to 98 minutes at 130 C. Examples 10 to 16 To harden a system which consists of 100 parts

  an epoxy resin of average molecular weight, equi-

  350 epoxide, and 30 parts of tetrahydrofuran anhydride.

  phthalic, it takes 39 minutes at 130 ° C. to reach state B.

  By adding 4 parts of 4,4'-bis- (3-phenyl-6-methyl)

  leimido-quinoxaline-2-yl) -diphenyl to this system,

  to B min at 130 ° C the time necessary to reach the state B s the respective values of A and B are shown in Table 1 below t

Table 1

Example 10 11 12 13 14 15 16

parts of bis-salt

  imide added, A 0 1 3 6 10 15 20 30 duration B, mn 39 37 32 25 21 15 10 6 Examples 17 to 19 To cure a system consisting of 100 parts

  an epoxy resin of average molecular weight, equi-

  350 epoxide, and 30 parts of tetrahydrofuran anhydride.

  phthalic, it takes 39 minutes at 130 C to reach the state B. By adding A parts of 1,4-bis- (maleimido) -bensene to this mixture, is lowered to B min at 130eC the time required to achieve state B. The respective values of A and B

  are shown in Table 2 below.

12 2503169

Table 2

  Example 17 18 19 parts of added bis-maleimide, A 0 1 2 3 duration B, mn 39 32 30 26

Example 20

* To prepare a corpa molded from a molding material consisting of 100 parts of a low molecular weight epoxy resin, epexyde equivalent 190, and 70

  parts of phthalic anhydride, a duration of

  from about 15 h to 130 Co when 10 items are added

  4,4'-bis- (3-phenyl-6-maleimido-quinoxaline oxide)

  2-yl) -diphenyl, the curing time falls to less than 120 minutes. After 120 minutes of curing, the molded objects

  from the maize modified by the bia-maleimide presented

  tensile strength at flexural fracture of about N / mm2. By prolonging the curing time, this value is not modified. The Vicat temperatures of molded articles cured for different durations reach the following values: hr. 2 3 4 S 6 7 12 & 4

  T (OC) 128 139 138 138 140 137 146 146

  The quantity of water absorbed by x 50 x 4 m3 samples is as follows t 4 Daya 12 Days 20 days 40 days

0.57% 0.73%

00.25% o, 45%

13: 2503169

Claims (4)

  1 - reactive accelerators for anhydride-hardened epoxide resin systems, characterized in that they consist of bis-maleimides of the general formula 1 CH-co-CH xN N CH - CO R CO - CH in which R represents CO - CH2 CH2 - CO _ R - [N N - R CO - CH - NH - R - NH - CH - CO   n has a value of 0 to 10, R and R ", which are identical or different, each represent one of the following radicals C6H4, C6H4 C6H4-CH2-C6H4 C6H4-0-C6H4 C6H4-C6H4-S02 C C6H4, C3H6, C6H4 C6H4-CH (C6H5) -C6H4 C6H4, C6H4-C6Ho1 C 6H4-CO-C6H4 1,3-C6H4 1,4-C6H4 C2H4 2B4 C6H10 C6H1o-CH2-C6H10 CH 2 -C 6 H 10 -C 6 H 10 CH 2 1,3- (CH3) 2-C6H2 1,4- (CH3) 2-C6H2 LE6H4-C2N2 (c6H5) -C6H3_720 14 2503169   2 - reactive accelerators beJsen claim 1, characterized in that they are added in amounts of   0.5 to 30% of the total weight of the resin-hardener system.   3 - reactive accelerators according to claim 1, characterized in that the curing, in the first operating stage, is preferably carried out by heating at a temperature of 100 to 220 C in a period of time from l mn to 30 mn.   4 - reactive accelerators according to claim 1, characterized in that they are used where appropriate with auxiliary catalysts.   - reactive accelerators according to claim 1 or 4, characterized in that the auxiliary catalysts   are tertiary amines, Lewis acids, poly-   alcohols, chromium, cerium, titanium and   zirconium of carboxylic acids or derivatives of poly- mercaptans.