DE1298715B - Process for the production of coverings and coverings based on epoxy polyadducts - Google Patents

Description

In British Patent 789,475 there is a method for reacting epoxy compounds with a complex formed from a resole and a polyamine, which contains at least two active hydrogen atoms forming part of the amino or imino groups. Such reaction components are formed by the products of the interaction of phenols, aldehyde and amines, wherein phenolic alcohols are initially characterized by the interaction of Phenols and aldehydes are generated in alkaline solution. The products are then reacted with polyamines to form a complex that has more than two active hydrogen atoms per molecule, which are bonded to nitrogen atoms contains.

In British patent specification 868 892, mixtures are also described which contain an epoxy compound and contain as a reaction component the product which is produced by reaction of a phenol, an aldehyde and a polyamine either by adding the aldehyde to a phenol-polyamine mixture or by adding the phenol to an aldehyde-polyamine mixture in such a way that the reaction product has at least 3 active hydrogen atoms bonded to nitrogen atoms, contains, is obtained. Such mixtures likely contain predominantly compounds that one or contain several aminated side chains and their formation by the presence of a high molecular ratio of amine and formaldehyde to phenol is promoted.

It is also known to use epoxy compounds with amines in the presence of coal tar and coal tar pitch to implement.

The invention relates to a method for producing coatings or coverings on the Base of polyadducts by reacting epoxy compounds that have more than one epoxy group contained in the molecule, and amines in the presence of coal tar or coal tar pitch, which thereby is characterized in that condensation products are used as amines, the total of more than contain two active hydrogen atoms on the nitrogen atoms in the molecule and those from one or polyhydric phenols, formaldehyde or furfuraldehyde, and polyhydric aliphatic amines have been manufactured.

The condensation products expediently contain a total of more than 2.5 active hydrogen atoms.

Epoxy compounds containing terminal epoxy groups are generally more reactive and to implement at lower temperatures than others. These epoxy compounds include the generally commercially available epoxy compounds such as diglycidyl ether of diphenylolpropane and such compounds as butadiene dioxide and vinyl cyclohexene dioxide. They have that in common Feature that they have an aliphatic chain with an epoxy group at the two terminal ends Carbon atoms.

Compounds containing so-called internal epoxy groups can also be used, such as bis (2,3-epoxycyclopentyl) ether and 3,4-epoxy- - methyl - cyclohexyl - methyl - 3,4 - epoxy - 6 - methylcyclohexanecarboxylate.

The coal tar used in the method according to the invention is a known bituminous product that accrues in the decomposition distillation of coal or coke. It includes tar made by high or low temperature processes obtained in horizontal and vertical retorts or coke ovens. Both raw tar and different types of refined tar can be used Tar including road tar can be used. Coal tar pitch, which in the invention Method used includes the residues that arise when using the permitted coal tar types be distilled. It is understood that the distinction between refined tar and Pitch is arbitrary and depends mainly on viscosity and melting point. The term coal tar pitch is usually applied to a residue that has a ball and ring melting point of 35 ° C or above.

The amine condensation product can e.g. B. be prepared in a known manner by a Reacts phenol with an aldehyde in alkaline solution and then the product with a Polyamine converts. Another known method of making the condensation product is by first mixing the phenol with the polyamine and then slowly adding the aldehyde, while continuously cooling the reaction mixture. A well-known variation on the latter method consists in first mixing the aldehyde and the polyamine and then slowly and continuously Cool the phenol adds. When using all of these methods it is necessary to determine the proportions of the reactants to be dimensioned so that the end product in total more than 2 and preferably more than 2.5 contains active hydrogen atoms bonded to the nitrogen atoms in the molecule.

The aldehyde is formaldehyde or furfuraldehyde and the phenol can be monohydroxybenzene, m-cresol or 1: 3: 5 xylenol.

The polyvalent aliphatic amines can be hexamethylene diamine or tetraethylene pentamine be.

Epoxy compounds with more than one epoxy group in the molecule are therefore particularly advantageous, because they can be converted quickly and at low temperature and because polyadducts obtained from them react in a satisfactory manner under unfavorable conditions. Therefore, for example at low room temperatures, such as, for example, 15 ° C. or below, satisfactory conversion rates can be obtained. In addition, such coatings and coverings can be underneath create damp or wet conditions, or even actually underwater. If they have diluents such as sand, stone or quartz, the reaction is caused by the dilution of the epoxy compound and retards, but nonetheless, the spreading in the form of a thin film such coatings have fast reaction speeds under the conditions mentioned low temperatures.

According to the invention, coverings can be produced where a rapid reaction rate occurs low temperatures and under humid conditions is advantageous, e.g. B. with a non-slippery one Road surface showing very good abrasion resistance.

In other cases where rapid implementation at low temperatures is not so important, for example with Joining cables and cheap corrosion-resistant coatings applied to steel

are to be, the coatings produced according to the invention can also be used with advantage.

The coatings and coverings produced according to the invention have low temperatures at room temperature and a higher conversion rate under water than analogous compounds coatings which instead of the condensation products used according to the invention are diethylenetriamine contain. For example, a covering produced according to the invention takes less than 48 hours was completely reacted at -5 ° C, a corresponding coating containing diethylenetriamine was even not fully implemented after 96 hours.

The method according to the invention is explained in more detail by the following exemplary embodiments.

The term "parts" in the description means "parts by weight".

example 1
A conversion component A was made

Hexamethylenediamine 1 mole

Formaldehyde (37 percent by weight / wt.

Formalin) 1 mol

Phenol 1 mole

manufactured. The phenol and hexamethylenediamine were mixed and the formalin added continuously while stirring and cooling so that the temperature was maintained at 35 to 40 ^° C. After the addition of the formaldehyde had ended, the reaction mixture was ^{heated to 100 °} C. and water was removed by distillation under reduced pressure.

An expanded epoxy mix suitable for paving a road was used from

Parts

Epoxy compound, which mainly consists of
the diglycidyl ether of diphenylol

propane is 100

Coal tar (tar from a vertical retort with low aromatic content,
that with Creosot to a viscosity of
800 seconds, Redwood No. 1 at

37.78 ⁰ C was blended) 100

Implementation component A 50

Silica flour 50

manufactured.

The coal tar, component A, and silica flour were mixed first. The premix and epoxy compound were then mixed and spread over the road and an aggregate was spread evenly over the pavement. The mixture was reacted at a temperature of +4.44 ⁰ C to give a viscous non-slippery surface.

Example 2

A conversion component B, similar to that for the conversion component A in Example 1, was used with the difference that the following substances were used:

Tetraethylene pentamine 1 mole

Formaldehyde (37 percent by weight / wt.

Formalin) 2 mol

Xylenol (boiling range 215 to 230 ° C) ... 2 mol

It was an elongated resinous epoxy mix used for sealing cable joints is suitable using

Epoxy compound consisting mainly of the diglycidyl ether of diphenylolpropane and a plasticizer component is 100

Coal tar (tar from a vertical retort with low aromatics content, which is blended with creosote to a viscosity of 800 seconds Redwood no. 1 at 37.78 ⁰ C) 50

Implementation component B 50

Silica flour 50

manufactured.

The coal tar, the reaction component and the silica flour were premixed. there has been a Form brought around the cable connection point and the mixture of epoxy compound with the premixed Pitch / conversion component / silica flour poured into the mold, which quickly reached about 7.22 ° C converted to form an excellent insulation layer around the joint.

Example 3

A reaction component C was prepared as follows.

A hexamethylenetetramine-catalyzed resole was first prepared by equimolecular Quantities of phenol and formaldehyde have been converted. Then the implementation component made by

Resol 3MoI

Diethylenetriamine 1 mole

15 minutes at 7O ⁰ C and then 15 minutes at 100 ° C were implemented. The reaction mixture was then distilled under 63.5 cm vacuum at 100 ° C and held at 90 ° C before removing the resinous product.

An epoxy mixture, which is suitable as a corrosion-resistant coating for steel, has been used

Made using the following components:

Epoxy compound made from a solid condensation polymer of diphenylolpropane and epichlorohydrin

stands 12.2

Xylene 12.6

Sec. Butanol 12.6

Coal tar pitch (coke oven pitch with a ring and ball softening point of 26.11 ° C, specific gravity 1.226 at 15.5 ° C and 10.3% insoluble in

Carbon disulfide) 36.6

Asbestine 24.9

Aerosil 1.1

Conversion component C 6.1

Cellosolve 4.3

Toluene 2.3

n-butanol 2,3

The epoxy compound was heated in the mixture of xylene and sec. Butanol dissolved. The coal tar ^{pitch was heated to 50 0} C and added to the epoxy solution, the mixture 15 Mi-

utes has been thoroughly stirred. The asbestine and diethylenetriamine 1 mol

Aerosil were added with vigorous stirring, formaldehyde (37 percent by weight /

to form a coating base. The um- wt. Formalin) 2.6 mol

Settlement component was heated and with the phenol 2.6 mol

Mixture of toluene-butanol-cellosolve diluted 5

and this was used with the coating base.

mixes before it is applied to a steel plate It was a resinous epoxy mix that

became. is suitable for sealing cable connections,

B is ρ ie 1 4 ^using

Conversion component D was made up of “... .. _π · · 1 <1 ^parts

^{6 F} epoxy compound as in Example 1

Hexamethylenediamine 1 mole wrote 100

Furfuraldehyde 1.1 mol conversion component F 83

Xylenol (boiling range 215 to 23O ⁰ C) .. 1.1 mol coal tar (tar from a vertical retort

ν _t ju ^I5 with a low aromatic content, which with

It was an elongated resinous mixture, the £ ™ £ S ^ SdSffS 3778 ⁵ C iS "

is suitable for occupying a street, after the u · « .? ^ ^{ood Nr> l at J7 '78 L ver} " ™

Example 1, but you are fine

in that conversion component A is produced by conversion 20.

component D was replaced. The mixture was as described in Example 2

and completely converted at room temperature

Example 5 set.

A solvent-free coating mixture was obtained
low viscosity prepared by A reaction component F was prepared

Share ^out

Vinylcyclohexendioxyd 76 tetraethylene pentamine 1 mol

Reaction component A (produced formaldehyde (37 percent by weight / wt.

as described in Example 1) 85.5 ³ ° formalin) 1 mol

Coal tar (tar from a vertical re-t-butylcatechol (t-butylcatechol) .. 1 mol

low aromatic cake, _ ^ _tD ,., ... j ^. ...-. ,

with the creosote to a viscosity of ^the t-Butylbrenzcatechm and Tetraathylenpent-

800 seconds, Red ood No. 1 at amm were mixed and ^{heated to 6O 0} C,

17 7R ° r vprcr-hnittpn \ <t \ 1? 35 b «s the t-butylpyrocatechol had dissolved. then

the formalin was added continuously in the course of IV2 hours with stirring and cooling,

mixed. so that the temperature was maintained at 60 to 65 ⁰ C.

The resulting mixture had a lifetime. After the addition of the formaldehyde in excess of 8 hours but continued satisfactory 40 was completed, the reactive mixture in 36 hours, to form a hard, tough 30 minutes at 65 ° C maintained and then at 100 ⁰ C the coating in order. heated and water by distillation under reducing

tem pressure removed.

Example 6 The product was a clear, dark brown, viscous

45 ser semi-solid. This was in furfuryl alcohol

A hot-reacting coating mixture in the ratio of 100 parts of product to 15 parts was obtained Low viscosity made by dissolving furfuryl alcohol.

_T .. As in Example 2, a stretched epoxy

Bis- (2,3-epoxycyclopentyI) -ether 9Γ mixture, which is used for sealing cable connections

^{Conversion component} A 85.5 ⁵ ° £ ^un S ^{en ei} f ^et ' unter [ Use of the following

Coal tar pitch (coke oven pitch made with one component.

Ring and ball softening point of ..

26.11 ⁰ C, specific weight 1.226 epoxy compound, essentially

at 15.5 ^C and 10.3% insolubles in a diglycidyl ether of bisphenol A.

Carbon disulfide) 35 ⁵⁵ consisting of 100

mixed. The life of the mixture for coal tar was (tar from a vertical retort

Room temperature for 3 days, but the ^solution-low aromatic content, which with

medium-free coating mixture provided when it creosote to a viscosity of 800 se-

60 to 90 minutes was ^{heated to about 100 °} C., 60 years is blended, Redwood No. 1

a tough, tough, chemically resistant oei J /, »cj ι χι

Coating implementation component F 41

° 'Siliciumdioxydmehl 50

Example 7

There was a conversion component F, similar to 65 B e i s ρ i e 1 9

as in Example 1 for conversion component A A conversion component G in

was described, produced with the difference, similar to the way above for implementation compo-

that the substances nente F in Example 8 was described

with the difference that the following substances were used:

Tetraethylene pentamine 1 mole

Formaldehyde (37 percent by weight / wt.

Formalin) 1 mol

Bisphenol A 1 mole

The product was a clear, dark brown, viscous semi-solid which was converted into furfurylaldehyde in the ratio of 100 parts of product to 15 parts of furfuryl alcohol was dissolved.

It was an elongated mixture that is suitable as a corrosion-resistant coating for steel, manufactured using the following components:

Parts

Epoxy compound consisting of a solid condensation polymer of diphenolpropane and epichlorohydrin is ... 12.2

Xylene 12.6

Sec. Butanol 12.6

ι coal tar pitch (coke oven pitch with ring

■ and sphere - softening point of

26, Γ C, specific gravity 1.226 at

15.5 ° C and 10.3% insolubles in carbon

fuel disulfide) 24.9

Asbestine 24.9

Aerosil (from Bush, Bech and Segner Bai-

ley Ltd.) 1.1

Implementation component G 2.6

The epoxy compound was in a mixture of xylene and sec. Butanol dissolved with warming. The coal tar pitch was heated to 50 ⁰ C and added to the Epoxydlösung, wherein the mixture stirred thoroughly for 15 minutes. The asbestine and aerosil were added with vigorous stirring to form a coating base. The reaction component G was mixed with the coating base before it was applied to a steel plate.

The test results of coating mixtures with conversion components according to Examples 8 and 9 are compiled in the following tables:

Table I 5 ° C

Implementation
component tar approach Appearance
(24 hours) <
24 Shore hardness
48
hours 96 Remarks 1
2 HA. 2
HA. 2 A.
B. hard and shiny,
a bit sticky
hard and shiny,
not sticky 93/80
90/50 95/85
90/65 94/90
95/92 hardened and totally custom
cash in just over 48 hours
the
a little slower than above;
usable product in
less than 96 hours

Table II Readings at R. T.

Implementation
component tar approach Appearance
(24 hours) C.
24 Shore hardness
48
hours 96 Remarks 1
2 HA. 2
HA. 2 A.
B. shiny, sticky
shiny, soft and
sticky 80/45
65/15 83/63
60/0 92/84
92/70 initially a little slower than
DQ 19 159, but achieved
approximately in 96 hours
same hardening
the same

Table III underwater

tar approach Appearance 24 ahem hardness 96 Remarks Implementation
component (24 hours) 48 HA. 2 A. hard, surface 93/90 hours 93/93 no crater formation; her 1 streaky, black 93/90 tet and usable in and brown, brownish 24 hours Part could be scraped off HA. 2 B. the same 93/90 93/93 the same 2 93/92

909 527/487

Comments on the tables

(Parts mean parts by weight) Ueile mean oewicmsteiiej

1st row 18 774/1 90

Tar HA. 2 94

Talk 47

DQ. 19 159 45

2nd row 18 774/1 90

Tar HA. 2. _; 94

Talk 47

DET 12

ok

R. 18 774/1 is an epoxy compound, which consists mainly of the diglycidyl ether of diphenylolpropane and has an epoxy equivalent of _{and eme viscosity at 25} o _{Q of 120} 0OcP.

Tar HA. 2 is coal tar, which is generated by a Koksofenprozeß which is plasticized with a heavy oil (bp. 270-360 ⁰ C). Probably about 90% aromatics.

DQ. 19 159 is a xylene-formaldehyde-hexamethylenediamine complex.

DET is diethylenetriamine.

R. T. means room temperature.

R.H. means relative humidity.

Table IV
3.17 mm thick covering

conditions Implementation
component tar approach Appearance
(24 hours) 24 Shore hardness
48
hours 96 Remarks -5 ⁰ C DQ. 19159
DET HA. 2
HA. 2 1
2 Surface a bit duff
soft and rubber
good Γ90 / 75
75/60 96/96
80/67 95/95
88/86 fully hardened in we
less than 48 hours
even after 96 hours
not fully hardened

Table V

conditions Implementation
component tar approach Appearance 24 Shore hardness
I 48 96 Remarks (24 hours) hours Readings
at RT
(from
Table II) DQ. 19159
DET HA. 2
HA. 2 1
1 Surface a bit duff
sticky 90/62
50/35 90/90
78/62 95/90
88/82 fully hardened in
48 hours
even after 96 hours
not fully hardened Under-
water (from
Table III) DQ. 19159
DET HA. 2
HA. 2 1
2 hard, a little duff
on the surface
Layer of
damp tar,
under this
Layer hard and
blotchy 91/91
94/93 92/92
96/96 96/96
97/96 hardened in 24 hours
Heavy surface
harms

Comments on the tables

Implementation component 1

Bisphenol A 1 mole

Tetraethylene pentamine 1 mole

Formaldehyde (37 weight percent / weight formalin) 1 mol

Implementation component 2

t-butylcatechol 1 mole

Tetraethylene pentamine 1 mole

Formaldehyde (37 weight percent / weight formalin) 1 mol

approach
(Parts mean parts by weight)

Parts

A. R. 18 774/1 100

Tar HA. 2 100

Implementation component 1 52

B. R. 18 774/1 100

Tar HA. 2 100

Implementation component 2 41

RT means room temperature. R. 18 774/1 is an epoxy compound which consists in the 55th main of the diglycidyl ether of diphenylol- ^ _ propane and has an epoxy equivalent of 190 '"" and a viscosity at 25 ⁰ C of 1200 ocP. Tar HA. 2 is coal tar, which is generated by a Koksofenprozeß which is plasticized with a heavy oil (bp. 270-360 ⁰ C). Probably around 90% aromatics.

DQ. 19159 is a xylenol-formaldehyde-hexamethylenediamine complex.

Claims (1)

Claim: Process for the production of coatings or coverings based on polyadducts Implementation of epoxy compounds that more 11 12 contained as an epoxy group in the molecule, hydrogen atoms on the nitrogen atoms in the and amines in the presence of coal tar or molecule and which consist of one or more Coal tar pitch, characterized by phenols, formaldehyde or furfur- n e t that amines are condensation products of aldehyde and polyvalent aliphatic amines used, a total of more than two active 5 have been manufactured.