NL8800168A - COLD-CROSSING, FLEXIBLE AND / OR ELASTIC EPOXY ARTIFICIAL RESIN MIXTURES AND METHOD FOR THE PREPARATION THEREOF. - Google Patents

Description

ï NL 34.818-Kp / ab

Cold-crosslinking, flexible and / or elastic epoxy-synthetic resin mixtures and method for their preparation

The invention relates to cold-crosslinking, flexible and / or elastic epoxy synthetic resin mixtures, as well as to a method for the preparation of the synthetic resin mixtures.

The mixtures according to the invention are suitable for flexible or elastic bonding, for sealing expansion joints or for obtaining elastic coatings, due to their favorable expansion on stretch.

The epoxy resins are usually prepared from dian (2,2-bis- (4-hydroxy-phenyl) -propane) and epichlorohydrin (1,2-epoxy-3-chloropropane) in a basic medium. The epoxy resins are made up of linear oligomer molecules.

The molecular size determines whether the polymer is liquid at room temperature, has a low viscosity or is solid. The liquid and solid epoxy resins usually experience due to their epoxy groups at the chain end (at room temperature), respectively. as a result of hydroxyl groups introduced in the chain (in the heat) a conversion to 15 polymers with cross-linked structure. The cross-linked epoxy resins have excellent physical and chemical properties, which is why they also have numerous industrial applications.

The liquid "cold-curing" epoxy resins are used to protect surfaces of various materials (metal, concrete, wood), furthermore for adhesion, for insulation in the electrical industry, for obtaining coatings in construction, as well as for glass-reinforced plastics. The "heat-curable" solid epoxy resins mainly serve as a binder in the paint industry.

The epoxy resins known heretofore are usually hard and tough after cross-linking and thus cannot be used for a wide variety of purposes requiring flexibility and elasticity.

In the previous decades attempts have been made to flexibilize the .88001 i - 2 - y epoxy resins, respectively. elastic, but were found to be elastic due to their inadequate flexibility, respectively. large-scale elasticity to be unsuitable.

Two methods are generally known for flexibilizing epoxy resins. The so-called plasticizing from the outside (such as, for example, di-butyl phosphate). leads to flexibility, but the chemical resistance of the cross-linked product as well as the product quality is greatly reduced.

In case of so-called inner softening or flexibilization, the chemical structure of the epoxy resin is modified so that the chain length of the polymer segments grows, so that a more flexible or elastic polymer with low cross-linking density is obtained. The internal flexibility of the epoxy resins can take place in the epoxy resin itself, but also in the crosslinking components. The best known type of flexible epoxy resin is prepared from epichlorohydrin and polyglycols (Potter: epoxide resins, S.126. Iliffe Books, London).

However, the expansion of such flexible epoxy resins is only 10 to 30% greater than that of the hard tough epoxy resins. With a flexible cross-linking agent, eg polyazelaic acid or its anhydride, a flexible epoxy resin can also be prepared, which however is heat-curing (GB 1,016,354). The poly (aminoamide) on dimerized fatty acid base also gives rise to little flexibility, so that the cross-linking of the epoxy resins also takes place "in the cold" (at 19-25 ° C). In the field of flexible epoxy resins, further development has taken place in the previous 10 to 15 years, which leads to a further increase in the degree of flexibility. Such epoxy-rubber resins are prepared, for example, from dian-diglycidyl ether and dimeric fatty acids or a dicarboxylic acid prepolymer, the segment chain consisting of at least 14 members (eg -C1 groups). The so-called "epoxy telechelic prepolymer" thus recovered are semi-hard synthetic resins which are used in the heat or reactive diluents (e.g.

.8800168 ♦ - 3 - * mono- and di-glycidyl ether) dissolved can also be cross-linked in the cold. The preparation of epoxy rubber is described in FR 1,559,969 and US 3,173,971 and US 3,280,056. These epoxy resin blends have an elongation to elongation of 70-90%.

An object of the invention is primarily the preparation of an epoxy-synthetic resin mixture in an improved quality compared to the known epoxy resins, which, in addition to obtaining the known favorable properties of the epoxy resins - good adhesion, resistance to chemicals and atmospheric influences - have increased flexibility and / or elasticity, secondly developing methods by which simpler and more economical epoxy resin resins can be prepared compared to previously known methods with increased flexibility and / or elasticity.

The invention is partly based on the recognition that a flexibilization of the epoxy resin components and also of the crosslinking components of the mixture results in a product which, due to its flexibility and / or elasticity, is suitable for use in flexible and / or elastic adhesives , for sealing expansion joints or, for example, for obtaining coatings for sports grounds. It has further been found that low molecular weight liquid epoxy resins with poly (alkylene oxide) diglycols and semi-drying vegetable oils can chemically react at 140-180 ° C thereby obtaining a significant increase in the polymer molecular weight. The flexible epoxy resin obtained, alone or in combination with a normal liquid epoxy resin, with poly (aminoamide) cross-linking agents on a dimerised fatty acid basis results in an optimum setting of the segment length and the cross-linking density to a cold-setting flexible and / or elastic synthetic resin.

The object of the invention consists of cold-crosslinking, flexible and / or elastic epoxy resins, which contain a condensate, consisting of 40-50 parts by mass of epoxidized phenolic resin and / or epoxidized 2,2-bis (4-hydroxy-.880016b «» - 4 -

a

phenyl) propane, with 185-220 epoxy equivalent and a viscosity of 3-15 Pa.s / 25 ° C, 10-25 parts by weight of mono- or diglycidyl ether or 10-25 parts by weight of carboxylic glycidyl ester, 15-20 parts by weight of poly (alkylene oxide) diglycol with molecular masses of 200-600 and 15-20 parts by weight semi-drying or non-drying vegetable oil, further 0-500 parts by weight of a starting grade epoxy resin, as well as 20-700 parts by weight. poly (amino amides) with a viscosity of 5-25 Pa.s / 25 ° C and an amine number of 350-450 or poly (ether urethanamine) with a viscosity of 4-6 Pa.s / 25 ° C and an amine number of 120 -150, possibly mixed with mineral and / or organic fillers.

The process according to the invention is carried out as follows: 40-50 parts by mass of epoxidized phenolic resin and / or epoxidized dian with an epoxy equivalent of 185-220 and a viscosity of 3-15 Pa.s / 25 ° C, 10-25 parts by mass are condensed. mono- or diglycidyl ether or carboxylic acid glycidyl ester with 10-20 carbon atoms, 15-20 parts by weight poly (alkylene oxide) diglycol with a molecular weight of 200-600 and 15-20 parts by weight semi-drying or non-drying vegetable oil at 140-160 ° C for 1-3 hours, which mixture is optionally allowed to react after 30-60 minutes at a pressure of 0.001-0.01 MPa. The obtained flexible and / or elastic epoxy resin with 250-600 epoxy equivalent and a viscosity of 25 0.1 Pa.s / 25 ° C is combined with 0-500 parts by mass of epoxy resin thereof of initial quality, after which the mixture is cross-linked with 20-700 parts by mass poly (aminoamide) with a viscosity of 5-25 Pa.s / 25 ° C and an amine number of 350-450 or poly (ether urethanamine) with a viscosity of 30 4-6 Pa.s / 25 ° C and an amine number of 120-150 and optionally with mineral or organic fillers.

The epoxy resins used in the mixture and in the process of the invention should have a low molecular weight and a liquid consistency. Epikote 828 (product of Shell Chemicals), Araldit GY-280 (CIBA AO product), NOVEPOX-380, NOVEPOX-302 (Kemik & l product, Hungary) are advantageously used as the epoxy resin.

.8800168 * - 5 - *

The liquid flexible epoxy resin obtained after condensation has an epoxy equivalent of 300-500 and a viscosity of 0.2-2 Pa.s / 25 ° C.

The flexible product is advantageously mixed with the crosslinking components alone or with the starting epoxy resin in a ratio of 10: 1-50.

The epoxy resin used for joining can be diluted with 20-50% by mass of mono- or diglycidyl ether - e.g. phenyldiglycidyl ether, 2-ethylhexylglycryl dyΙ-ΙΟ ether, butanediol diglycidyl ether.

For cross-linking, poly (aminoamide) on a dimerized fatty acid base is used, preferably Versamide 140 or poly (ether urethanamide), preferably Euradur-X-75.

100 parts by mass of the flexible intermediate epoxy resin are preferably mixed with 20-50 parts by weight poly (aminoamide) or 100-120 parts by weight poly (ether-thanamine).

The main technical characteristics of the crosslinked flexible and / or elastic epoxy resins are: 20 tensile strength 1-50 N / m ^ expansion at elongation 50-450% water absorption 3-5%

The preparation of the mixtures according to the invention is illustrated by the following examples:

EXAMPLE I

400 kg of liquid, heated epoxy resin (eg Epikote-828) and 30 kg of 2 kg (2-ethylhexyl) glycidyl ether were weighed in a downcomer condenser equipped with a vacuum connection and 1250 l volume, followed by a short stirring of another 150 kg of castor oil and 150 kg of polyethylene glycol (molecular weight: 200) were added. The auto-clover contents were heated to 140-150 ° C, at which temperature the reaction mixture was stirred for 2 hours. After the completion of the reaction, the contents of the autoclave were cooled to 20-25 ° C and the recovered 890 kg of liquid resin was transferred to a container.

. 88 0 0 1iP

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The main characteristics of the flexible epoxy resin were:

viscosity 0.4-1 Pa.s / 25 ° C

epoxy equivalent 350-400 5 A 2-component adhesive can be prepared from the resulting epoxy resin, the component "A11" being composed of 100 parts by mass of flexible epoxy resin, 35 parts by weight of the starting epoxy resin (eg Epi-10 kote 828), 15 parts by weight of phenylglycidyl ether. prepared by simply mixing together.

The component 11B "consists of 60 parts by mass of liquid poly (aminoamide), 15 with the characteristics: amine number: 400-450 mg KOH / g viscosity: 10-20 Pa.s / 25 ° C.

The mixing ratio of the components "A": "B" of the adhesive resin is: 2.5: 1.

The adhesive resin is applied in an amount of 0.5-0.7 kg / 2 m to concrete soil of. a sports field, after which 10-15 mm thick rolled top layer is applied on top of the adhesive resin. The adhesive layer is bound after 24 hours so tightly that the sports field is running. Full binding is reached after 7-10 days.

The epoxy adhesive according to the invention can also be used to seal the expansion joints of the sports field coating.

EXAMPLE. II

In the synthetic resin cooking device according to example I

400 kg epoxy resin with the following characteristics: bisphenol A / F based, epoxy equivalent of 195-205, viscosity 3-6 Pa.s / 25 ° C 35 (prepared according to Hungarian patent no. 180,488) 200 kg C . | ^ -tertiary fatty acid glycidyl ester (eg "Cardur a-E 10"). 8 8 0 o -7-- Λ 150 kg polyethylene glycol (Mg: 200) 150 kg castor oil.

The reaction mixture was treated at 140-160 ° C for 2 hours, followed by pressure reduction to 0.01 MPa, then condensation continued for an additional 30 minutes; finally, the mixture was cooled to room temperature, the resulting 800 kg of flexible epoxy resin being transferred to a container. The aqueous phase collected in the receiving flask was transferred to a water tank.

The main characteristics of the product were: epoxy equivalent 400-500

viscosity 2-3.5 Pa.s / 25 ° C

A 2-component agent for sealing expansion joints was prepared from the flexible epoxy resin.

The component 11A "is obtained by simply mixing together 100 parts by weight of flexible epoxy resin with 36 parts by weight of normal epoxy resin (Example I). 15 parts by mass of 2-ethylhexyl glycidyl ether.

The component "B" consists of 60 parts by mass of poly (aminoamide) (example I).

The mixing ratio of the components "A": "B" is 2.5: 1.

The mixed resin is poured into the 6-8 mm wide and 5-25 mm deep expansion joints of the ceramic coating already laid, which resin is allowed to solidify for 24 hours.

The main characteristics of the cured dilatant were: 2 tensile strength 6-12 N / mm 30 expansion at stretch 150-200% water absorption max. 4.0% / 4 weeks

EXAMPLE III

In the device according to example I and according to the described preparation method, the flexible epoxy resin was prepared. The composition of the reaction mixture was as follows: 400 kg of epoxy resin (according to example II) 200 C10 tertiary fatty acid glycidyl ester ("Cardura-E-10") • 8 8 OU i - r »- 8 - 150 kg of poly (propylene oxide) -diglycol (Mg: 400) 150 castor oil

The characteristics of the resins obtained are: epoxy equivalent: 250-350

Viscosity: 0.1-0> 3 Pa.s / 25 ° C

A 2-component expansion joint sealant was prepared from the flexible epoxy resin. The composition of the component "A" is: 80 parts by mass of the flexible resin 10 16 parts by mass epoxy resin (example I or II) 4 parts by mass (2-ethylhexyl) glycidyl ether.

The composition of the component "B" was: 40 parts by weight poly (aminoamide) (Example I) 10 parts by weight poly (aminoamide) (reammide-PG5-50)

Viscosity: 5-10 Pa.s / 25 ° C

amino number: 300-350

The mixing ratio of the components "A": "B" is 2: 1.

Expansion joint sealing was performed in a similar manner as in Example II.

20 The characteristics of the cured fabric were: 2 tensile strength: 2-4 N / mm expansion at stretch: 150-250% water absorption: max. 2.5%

EXAMPLE IV

The flexible epoxy resin was prepared in the device according to example I and with the composition according to example III.

From the flexible epoxy resin obtained, an elastic expansion joint sealant was prepared with the composition of the component "A": 100 parts by mass of flexible epoxy resin 200 parts by mass of normal epoxy resin ·

Composition of the component "B": 400 parts by mass of poly (ether urethanamine) (eg.

35 Euredur X-75)

Characteristics: amine number: 130

viscosity: 4.5-5.5 Pa.s / 25 ° C

.8800168 4 - 9 -

The mixing ratio of the components "A": UB "is 1: 1.3.

The main characteristics of the solidified epoxy resin were: 2 tensile strength: 2-4 N / mm expansion at stretch: 300-500% 5 water absorption: max. 3%

With the flexible epoxy resin according to example IV, an elastic 2 or 3-component pavement or sports field covering with the following composition was produced:

Component "A" 10 100-400 parts by weight flexible resin 100-200 parts by weight epoxy resin 100-300 parts by weight mineral / filler (eg quartz flour, quartz sand)

Component MBW

15 250-400 mass parts of cross-linking agents (e.g.

Versamid-140, Euredur X-75, Reammide-PO5-50)

Component "C" 100-600 parts by mass of elastic filler (eg.

20 truck tire regrind, EPDM rubber regrind)

The mass gained by mixing the components A: B: C in the required ratio was applied to the sufficiently solid pavement or sports ground substrate in a thickness of 2-25 mm. After 24 hours of binding time, the coating was found to be tensile, while after 10-14 days, the coating was found to fully meet the requirements.

The favorable flexibility / elasticity properties of the mixtures according to the invention compared to the known flexible epoxy resins are demonstrated by means of Example V.

EXAMPLE V (comparative example)

The liquid epoxy resin was prepared by a modification with castor oil and flexible resin (product EPOTÜP-37-151 from Reichhold Chemie AG) with the following main characteristics:

viscosity: 30-50 Pa.s / 25 ° C

epoxy equivalent: 500-550 .8800168 2 c - 10 -

Characteristic properties after cross-linking: tensile strength: 5-6 N / mm elongation at elongation: max. 50% EXAMPLE VI (comparative example) 5 According to U.S. Pat. No. 3,173,971, a flexible epoxy resin was prepared from 2 moles of bisphenol-A diglycidyl ether or low molecular weight oligomer (e.g. epoxy resin normal Bpon-828) with 1 mol dimer fatty acid (e.g. linoleic, linolenic acid dimer with 34 carbon atoms, Commercial Product "Empol-1014") a "telechelic prepolymer". The flexible / elastic resin thus obtained (e.g., Handelsproduct Epikote-872), Shell Co.) had the following main characteristics: consistency: semi-hard resin

Viscosity: 1.5-3 Pa.s / 25 ° C

(75% solution in xylene) epoxy equivalent: 650-750

The semi-hard resin was brought into a liquid consistency with 10-20% mono- or di-glycidyl ether and then solidified with various cross-linking agents.

Main characteristics of the obtained epoxy elastomer were:

Type of cross-linking tensile hard expansion ίγ strength at 25 N / mm2 shore A elongation% aliphatic polyamine diethylene triamine 1.3 87 35 O.

trimethylhexamethylene-diamine 2.5-5 60-90 70-90 isophorone diamine (cycloaliphatic amine) 1 ”5 55-80 100-250 .8800168 <·« 11 - * 5 EXAMPLE skin (comparative example)

A normal liquid epoxy resin (eg Epikote-828, Araldite-GY-250, NOVEPOX-380) with the main characteristics:

5 viscosity: 5-15 Pa.s / 25 ° C

epoxy equivalent: 185-205 was solidified with the cross-linking agent polyaminoamide ("Verzamide 140") in the mass ratio 100: 50.

The characteristics of the obtained mixture 10 were: 2 tensile strength: 50 N / mm

hardness: 100 Shore A.

elongation at elongation: 0-0.5% EXAMPLE VIII (comparative example) A normal liquid epoxy resin (according to Example VII) was cured with a crosslinking agent of poly (ether urethanamine) type (Euredur-75) in a mass ratio of 100: 130. The resulting flexible epoxy mixture had the following characteristics: tensile strength:> 5-15 N / mm

hardness:> 100 Shore A.

expansion at elongation: 60-120% 25. 8 8 Ü D 1 £ t

Claims (7)

1. Cold-crosslinking, flexible and / or elastic epoxy-synthetic resin mixtures, in particular for sticking or sealing expansion joints or for the preparation of coatings, characterized in that they contain the condensate of 40-50 parts by mass epoxidized phenolic resin with an epoxy equivalent of 185-220 and a viscosity of 3-15 Pa.s / 25 ° C and / or of epoxidized 2,2-bis (4-hydroxy-phenyl) -propane, 10-25 parts by weight mono - or diglycidyl ether or a carboxylic acid diglycidyl ester with 10-20 carbon atoms, • 10 15-20 parts by weight of poly (alkylene oxide) diglycol with a molecular weight of 200-600, and 15-20 parts by weight of non-drying or semi-drying vegetable oil, 0-500 parts by weight epoxy resin of starting quality as well as 20-700 parts by mass of poly (aminoamide) with a viscosity of 5-25 Pa.s / 25 ° C and with an amine number of 350-450 or poly (ether urethanamine) with a viscosity of 4-5 Pa. s / 25 ° C and the amine number of 120-150, optionally with mineral and / or organic fillers. 2. Mixture according to claim 1, characterized in that they contain in the mass ratio 1: 0.2-1.3 epoxy groups-containing resin and poly (aminoamide) or poly- (ether urethanamine). Mixture according to claims 1 and 2, characterized in that it contains poly (alkylene oxide) -dlyglycol polyethylene glycol with a molecular weight of 200 or 25 poly (propylene oxide) diglycol with a molecular weight of 400. 4. Mixture according to claims 1-3, characterized in that as mono- or diglycidyl ether phenyl or (2-ethylhexyl) glycidyl ether, butanediol diglycyl ether and as carboxylic glycidyl ester, tertiary fatty acid glycidyl ester with 12 or Contains 17 carbon atoms. 5. Mixture according to claims 1-4, characterized in that it contains linseed oil stand oil as semi-drying vegetable oil and castor oil as non-drying vegetable oil. .8800168 - 13 - * .i 6. Mixture according to claims 1-5, characterized in that it contains quartz flour with grain size of 0.001-0.4 mm, quartz sand as mineral filler, and motor vehicle tire regrind with organic grain size of 5 mm or less as organic filler. 7. Process for the preparation of cold-crosslinking, flexible and / or elastic epoxy resin mixtures, in particular for bonding or for sealing expansion joints or for obtaining coverings, characterized in that 40-50 parts by mass are epoxidized phenolic resin with an epoxy equivalent of 185-220 and a viscosity of 3-15 Pa.s / 25 ° C and / or epoxidized 2,2-bis (4-hydroxyphenyl) -propane, 10-25 parts by weight of mono- or diglycidyl -ether or carboxylic acid glycidyl ester with 10-20 carbon atoms 15 15-20 parts by mass poly (alkylene oxide) -diglycol with 200-600 molecular weight and 15-20 parts by weight semi-drying or non-drying vegetable oil condenses for 1-3 hours, then optionally 30-60 minutes long, at 0.001-0.01 MPa pressure after reacting, the obtained flexible and / or elastic epoxy resin with an epoxy equivalent of 250-500 and a viscosity of 0.1-1 Pa.s / 25 ° C mixes with 0-500 parts by mass of the epoxy resin of initial quality and subsequently to the mixture l 20-700 parts by mass of poly (aminoamide) - with a viscosity of 5-25 Pa.s / 25 ° and an amine number of 350-450 or poly (ether urethanamine) with a viscosity of 4-6 Pa.s / 25 ° C and an amine number of 120-150 and optionally adding mineral or organic fillers. 30 .6800168