DE102008014558A1 - Polycarboxylic acid modified native epoxides with a specific ratio of epoxide-polycarboxylic acid in glycidyl ester epoxide, useful for preparing polyether and polyester - Google Patents

Abstract

Polycarboxylic acid modified native epoxides, where the ratio of epoxide to polycarboxylic acid is 300:1-60:1 in glycidyl ester epoxide, is claimed.

Description

It is known that native epoxides can react with organic polycarboxylic acids or their anhydrides to form polyhydroxyesters or polyester networks ( DE 10 2006 060 917.4 . DE 4019 087 A1 and DE 4024 364 A1 ). The quantitative ratio of the two components is either equimolar or, in the case of special formations, 1: 1 / n-molar, which relates to the selected amount of polycarboxylic acid in relation to the amount of epoxide, but where n is chosen to be so small that no great differences in mass occur between the two material systems ( DE 198 34 048 ). Occasionally such epoxy-hardener mixtures in commercial form are commercially available as prepegs ( EP 0779904 . WO 2004 074 577 respectively. WO 2003 008 708 ).

It is also known that thermal energy is necessary to start the reaction, although both the Oxyranringöffnung base reaction and the subsequent polymerization run exothermic. This starting energy can also be applied by microwave radiation. However, it is necessary that the monomer units have enough OH groups as potential microwave resonators. If this is not the case, one can use interpenetrating polymers of the abovementioned EP resins and use the incipient polymerization of the native epoxides with the polycarboxylic anhydrides to generate in situ resonance sites in the so-called pre-gel phase, with the aid of which the entire mixture can be cured by means of microwave radiation ( DE 10 2007 006 776.5 ).

In addition to the above-mentioned 2-component resin-hardener formations, native epoxides can be polymerized under UV radiation in a 1-component manner, ie with themselves to give polyethers. With the use of soybean oil epoxides, takeoff rates of> 7.5 m / min are achieved in the polymerization or 13 m / min of caster oil epoxides ( JV Crivello et. al .: Chem. Mater. Vol. 4. 1992 692-699 ).

It is interesting that the products resulting from kite or h.Ω. linoleum oil epoxies have an exceptionally high chemical resistance, including alkali-resistant ( DE 10 2007 038 573.2 ). However, the adhesion of these polyethers on smooth surfaces, such. As glass or metal low. Conversely, polyester polymers adhere quite well to surfaces, but are not permanently stable to hydrolysis in native esters unless crosslinked with 3- or 4-membered carboxylic anhydrides (Table 1). Table 1: Property Maps of Polyesters and Polyols from Inactive Epoxies feature structure polyester polyether handling 2 components 1 part liability Good bad pot life limited unlimited alkali resistance bad very well MW curing quite possible not possible viscosity adjustable not adjustable Reactivity adjustable not adjustable

• • mit Polycarbonsäuren 2-komponentig zu Polyethern,
• • mit sich selbst mittels UV-Katalysatoren zu Polyethern.

Thus, native epoxides of high linolenic acid-containing oils can be polymerized into two product classes:

• With polycarboxylic acids 2-component to polyethers,
• • with itself by means of UV catalysts to polyethers.

Both Polymer classes have advantages and disadvantages, such as the comparison of Columns 2 and 3 in Tab. 1 identifies.

aim The present invention is to produce polyethers, the advantages Both systems both in the processing properties as well Own product properties.

• • eine kombinierte UV- und Mikrowellenanregung zur Erhöhung der Polymerisationsgeschwindigkeit,
• • 1-komponentige, Lösungsmittel freie Rezepturen,
• • Erhöhung der Reaktionsgeschwindigkeit photoinitiierter Etherpolymerisationen,
• • Erhöhung der Haftfähigkeit der Polyether und
• • variable Einstellung der Viskositäten der Epoxidharzformierungen.

The following goals are aimed for:

• A combined UV and microwave excitation to increase the rate of polymerization,
• • 1-component, solvent-free formulations,
• Increasing the reaction rate of photoinitiated ether polymerizations,
• Increasing the adhesion of polyethers and
• • variable adjustment of the viscosities of the epoxy resin moldings.

The Solution of this inventive task results This is due to the fact that in the epoxides a catalytically small amount of dicarboxylic or dihydroxydicarboxylic acids according to a dilution principle is polymerized into the epoxide.

Surprisingly, this does not lead to crosslinking polymerization at the point of entry if the acids to be introduced are slowly introduced in very high dilution, that is to say in a solvent of low solubility for the acid, and the epoxide is likewise present in dilute form. After reacting at the boiling point of the solvent, this is distilled off. This gives products whose viscosities in the range 300 ≤ η ⁴⁰ ≤ 2000 mm ² / s are given and thus can be adapted to the respective technical conditions at the processing of the epoxy resin mixtures.

For the not yet supported by microwave radiation photopolymerization, the rate of polymerization increases by the OH-groups formed during acid incorporation. They act catalytically on the oxirane ring opening. It is possible to follow this effect by IR spectroscopy on the increase in the polyether band at 1100 cm ^-1 . Compared with the pure epoxide, the extinction of this band increases significantly more rapidly in the case of the preprepared mixtures. The increase is in 1 at the extinction ratio of the bands v _ether / v ₁₂₄₄ cm ^-1 . As expected, it is the largest in the case of tartaric acid, because this acid itself contributes 2 OH groups to the α-hydro groups formed on the ester formation (upper curve in FIG 1 ).

mit:
R = 0, Alkyl
n = 0, 1, 2
MWR MikrowellenresonatorHowever, the introduced OH groups can act twice. In addition to the catalytic effect in the ring-opening reactions via H-bonding, they represent additional resonance sites for microwave radiation in a combined UV / MW-initiated polymerization. Ie. the heating and thus the speed of removal of the photopolymerization increase (equation 1).

With:
R = O, alkyl
n = 0, 1, 2
MWR microwave resonator

For the photopolymerization seems due to the loss of Oxyranringen First, this strategy to be counterproductive, since the Reaction rate depends on the Oxyranringkonzentration. Surprisingly However, it increases with high linoleic acid containing epoxides h.-Ω.-linseed oil or dragon's head oil the withdrawal speed in the photopolymerization to about 40 m / s. additionally takes the adhesion of these polymers on the surfaces to.

Since there are sufficient oxirane rings available for the polymerization in these epoxides with 6 to 8 oxirane rings per molecule, the sometimes feared termination reaction according to Eqs. 2 also no relevance ν:

Significant reaction acceleration is also achieved by adding a small amount of methyltetrahydrophthalic anhydride (MTHPA) to the epoxide. Traces of water that are always present in the epoxide due to the production process, provide traces of acid, which are the thermal reaction between epoxy and MTHPA starts. Subsequent UV irradiation results in a significantly faster reaction to polyethers, such as the increase in the viscosities to dependence of the reaction time in 2 shows.

• ¹⁾MV Massenverhältnis aus Polycarbonsäuremenge zur Epoxidmenge

Mixtures of linseed oil methyl ester epoxides with polycarboxylic acid can be prepared by the above-mentioned method (Table 2). They can be used, among other things, as reactive diluents for 1- or 2-component epoxy resin systems. Table 2: Concentrations and viscosities of linoleic methyl ester epoxy derivatives of maleic (MS), oxalic (OX) and tartaric acid WS concentration level MS OX WS MV ¹⁾ η ²⁰ in [mm ² / s] MV ¹⁾ η ²⁰ in [mm ² / s] MV ¹⁾ η ²⁰ in [mm ² / s] a 1:29 71 1:36 93 1:21 82 b 1:18 140 1:18 262 1: 10.7 296

• ¹⁾ MV mass ratio of polycarboxylic acid to the amount of epoxy

Experimental Procedure

Modified polycarboxylic acid native epoxides

• A

  Preparation of the copolymers

  A1

  Copolymers of glycidyl esters 3 g h.OMEGA.-linoleic glycidesterepoxide Type EP-10/1 are dissolved with 0.05 g of tartaric acid in acetone for 2 h at the boiling point of the acetone, then distilled off the acetone.

  A2

  3.2 g of linseed methyl ester epoxide with about 10% oxy-oxygen content are with 0.15 g of tartaric acid implemented and treated as described under A1 further.

  A3

  Similar to at A1 and A2, the copolymers of oxalic or maleic acid produced. The proportions are in the table 2 listed.

  B

  photopolymerization All Polymers are reacted with 1% UV catalyst of the type of triarylsulfonium hexafluoroantimonate or Phosphate polymerized with a Hg lamp at 365 nm.

  C

  Examination of the Photochemical Behavior of the Copolymers Mixtures containing 0.05 g of acid and 1% of catalyst per 3 g of EP-10/1 are irradiated with UV radiation according to B and in the interval of n × 1 min with n = 0.1 , ... 4 IR spectroscopy. For this purpose, the extinction ratio of the ether band at 1100 cm ^-1 to the reference signal at 1244 cm ^-1 and forms it against the time ( 1 ).

patent search

• DE 40 19 087 A1
• DE 40 24 364 A1
• DD 229 414 A1
• DE 101 54 364 A1
• DE 198 34048
• DE 10 2007 006 776.5
• DE 10 2007 0505 79.7
• DE 10 2007 038 573.2
• DE 10 2006 060 917.4
• EP 077 9904
• WO 2004 074 577
• WO 2003 008 708

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 102006060917 [0001, 0016]
• - DE 4019087 A1 [0001, 0016]
• - DE 4024364 A1 [0001, 0016]
• - DE 19834048 [0001, 0016]
• - EP 0779904 [0001, 0016]
• - WO 2004074577 [0001, 0016]
• WO 2003008708 [0001, 0016]
• - DE 102007006776 [0002, 0016]
• - DE 102007038573 [0004, 0016]
• - DD 229414 A1 [0016]
• - DE 10154364 A1 [0016]
• - DE 102007050579 [0016]

Cited non-patent literature

• - JV Crivello et. al .: Chem. Mater. Vol. 4. 1992 692-699 [0003]

Claims (9)

Polycarboxylic acid modified native epoxides, characterized in that the epoxide-polycarboxylic acid ratio min. [300: 1] to max. [60: 1] is the glycidosterone epoxides. Polycarboxylic acid modified native epoxides, characterized in that by the Polycarbonsäurezugaben the viscosities of the epoxy mixtures in the range: 300 ≤ η 40 ≤ 2000 mm 2 / s can be adjusted. Polycarboxylic acid modified native epoxides characterized in that the Absorbtionsvermögen in Microwave resonance of these epoxy mixtures by in α-position on the acid groups resulting or by the Einsynthetisieren of hydroxypolycarboxylic acids, d. H. With the number of hydroxyl groups formed or introduced in situ the resonance points increases. Polycarboxylic acid modified native epoxides characterized in that the additional OH groups the adhesiveness of the resulting UV radiation Polyether significantly improved. Polycarboxylic acid modified native epoxides characterized in that by the copolymerization of the polycarboxylic acids according to claim 1, the UV-initiated polymerization is accelerated. Polycarboxylic acid modified native epoxides characterized in that copolymers according to claim 1 in formal Analogy can be obtained from the methyl ester epoxides, where here proportions of: minute [36: 1] to max. [11: 1] be achieved. Polycarboxylic acid modified native epoxides characterized in that the polymers obtained according to claim 6 as a reactive diluent for 2-component epoxy resin formulations are suitable. Polycarboxylic acid modified native epoxides characterized in that mixtures according to claim 1 or 6 both to polyethers as well as polyesters can be polymerized. Polycarboxylic acid modified native epoxides characterized in that by the addition of small amounts of methyltetrahydrophthalic anhydride curing significantly accelerated after UV initiation.