EP2675846A2

EP2675846A2 - Curable polymer materials

Info

Publication number: EP2675846A2
Application number: EP12707975.4A
Authority: EP
Inventors: Dieter Rossberg
Original assignee: ThyssenKrupp Uhde GmbH
Current assignee: ThyssenKrupp Uhde Chlorine Engineers GmbH
Priority date: 2011-02-17
Filing date: 2012-01-25
Publication date: 2013-12-25
Also published as: US20130324642A1; WO2012110193A4; CN103380160A; CA2823064A1; WO2012110193A3; WO2012110193A2; JP2014513199A; KR20140037053A; DE102011011609A1; RU2013134620A

Abstract

The invention relates to a curable compound of a formulation according to the invention, to a method for producing a polymer material from the curable compound, to the resulting polymer material, and to agents produced from the polymer material according to the invention and the use thereof.

Description

Hardenable polymeric compositions

The invention relates to a curable composition of a formulation according to the invention, a method for producing a polymer material from the curable composition, the resulting polymer material, as well as agents which are made from the polymer material according to the invention and their use.

Curable compositions based on, for example, polyester resin,

Epoxy resins or polyamide are used to make articles reinforced with fibers such as glass or textile fibers, and are widely used in industry. Such plastic structures are materials made of

Reinforcing fibers exist, which are embedded in a plastic matrix. These are used in a variety of applications in the form of short fiber reinforced, long fiber reinforced or continuous fiber reinforced components use.

The subgroup of glass fiber reinforced plastics is a composite of a plastic, such as polyester resin, epoxy or polyamide, and glass fibers. Glass fiber reinforced plastics are standard materials in the industry. Tubes of this type are standardized in the DIN and commercially available.

In the field of alkaline media glass fiber reinforced plastics are mainly used to absorb or to alkaline liquids

transported. These are typically made with a thermoplastic material, such as e.g. Polypropylene, provided as a chemical protective layer. This chemical protective layer is present on those surfaces which come into contact with the alkaline solutions and is intended to protect the glass fiber reinforced plastics. This additional protective layer is required above all when the alkaline solutions have temperatures of> 40 ° C and thus their corrosive effect is enhanced and surfaces are attacked and destroyed.

At temperatures below 40 ° C and low concentrations of the alkaline media can be dispensed with a thermoplastic chemical protective layer and this is instead produced from the plastic matrix itself.

The disadvantage of the glass fiber reinforced plastics known in the prior art is that if the chemical protection layer is damaged, the glass fibers are exposed and exposed to a chemical attack by such media directly. Glass is a chemically highly resistant material, which, however, is not alkali-resistant and is massively attacked and destroyed by alkaline media of all kinds. By destroying the reinforcing fiber of the entire composite material is attacked, because the mechanical strength of the composite is due to the

Reinforcing fibers achieved. The elimination of mechanical strength leads to failure of the material, since the pressure and temperature load, the

For example, when operating an industrial plant prevails, no resistance is opposed.

A glass fiber reinforced plastic pipe according to the prior art is known for example from DE 10 2008 033 577 A1. In particular, this document teaches a plastic tube which has improved properties in terms of tightness, rigidity, dimensional stability and abrasion in comparison to the prior art. The pipe wall is formed by at least one in the spin and / or

Centrifugal casting method produced spin coating and at least one in the

Winding process produced winding layer. Although such pipes have improved properties, but are very expensive to produce.

For environmental technical reasons, it is necessary to develop compositions for such plastic pipes, which reduced at least one

Have metal concentration, or in which completely dispensed with the use of metals. In the prior art common metal concentrations

For example, the use of a 6% cobalt solution in concentrations of 0.5% based on 100% of a total mass to be cured. The from these

Compositions generated tubes should have lower removal rates than prior art tubes, which increases the life of such tubes.

In addition to a reduced removal of pipe materials a

Blockage of the pipes to be prevented by removed material.

The object of the present invention is therefore an alternative

Formulation for a hardenable mass, which has reduced metal concentrations, or is completely dispensed with the use of metals, the method for

Production of a polymer material from the curable composition and the

Polymer material itself to provide, the polymer material is a lower erosion rate when exposed to alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are to contain, as conventional polymer materials. The invention has also set itself the task of providing appropriate means and uses of the polymer material. The object is achieved by a cobalt-poor curable composition

full

, - a resin, in the form of epoxy novolac vinyl ester, wherein the resin in a

Concentration of 96.3 to 98.95% is included

a catalyst, wherein the catalyst is contained in the form of a 6% cobalt solution in a concentration of 0.05 to 0.1%,

an accelerator, wherein the accelerator is contained in the form of dimethylaniline in a concentration of 0 to 0.1%,

a hardener, wherein the hardener in the form of cumene hydroperoxide in a

Concentration of 1 to 2% is included

a UV stabilizer, wherein the UV stabilizer is contained in a concentration of 0 to 0.5%,

Paraffin, the paraffin being in the form of wax in a concentration of 0 to 1%.,

and the concentration data refer to 100% of a total mass to be cured.

Furthermore, the object is achieved by a metal-free formulation in which the curable composition comprises

a resin, in the form of epoxy novolac vinyl ester, wherein the resin is in a

Concentration of 94 to 97.95% is included

an accelerator, wherein the accelerator is contained in the form of Ν, Ν-dimethylaniline in a concentration of 0.05 to 0.2%,

a hardener, wherein the hardener is contained in the form of dibenzoyl peroxide in a concentration of 2 to 4%,

- A retarder, wherein the retarder is contained in the form of p-tert-butylcatechol in a concentration of 0 to 0.3%

Paraffin, the paraffin being present in the form of wax in a concentration of 0 to 1%,

and the concentration data refer to 100% of a total mass to be cured.

For example, commercially available from the company Ashland DERAKANE MOMENTUM ™ 470-300 for the resin epoxy novolac

Vinyl ester used. The accelerator can be added via the commercially available product PERGAQUICK A200 or A300 from Pergan. Of the Hardener is added via PEROXAN BP-Paste 50 or PEROXAN CU-80 L, which are also commercially available from Pergan. As retarder, for example, the product Pergaslow BK-10 is used. As UV protection, for example Tinuvin ^® 5050 ^® from Ciba can be used. The wax is eg BYK ^® -S 750 of the Altana Group. These products are to be understood by way of example and may be replaced by others which fall within the scope defined in claim 1 and in claim 2, respectively.

The method for producing a polymer material comprising the curable composition according to any one of claims 1 or 2, comprising the following method steps:

a. Resin and catalyst are subjected to pre-acceleration for a period not exceeding the expiration date of the resin,

b. the accelerator, hardener, retarder, UV stabilizer, paraffin in the

be added in the specified order, and a curable mass is generated,

c. wherein, depending on the formulation, one or more constituents of step b) and / or the catalyst of step a) are omitted,

d. the hardenable mass is brought into a desired shape by standard methods, whereby a workpiece is produced,

e. optional paraffin is applied to the workpiece from the outside, and

f. The workpiece is subjected to a heat treatment for 8 hours at 80 ° C and a finished polymer material is generated.

In the case of the metal-free formulation of the curable composition according to the invention, pre-acceleration is dispensed with in step a. of

process according to the invention, the addition of the catalyst is omitted.

Advantageously, further additional components, such as fillers and / or fiber materials, in particular glass fibers and / or glass fleeces and / or synthetic nonwovens are embedded in the curable composition.

Such glass webs are known from the prior art and standardized, and commercially under the name Textilgllasmatten for

Plastic reinforcement commercially available. It is advantageous to an aluminum borosilicate glass with a mass fraction of alkali <1% of the glass type E or to alkali-lime glasses with increased addition and special chemical

Resistance of glass type C. The invention further comprises a polymeric material comprising the ingredients of the curable composition of the invention based on the resin epoxy novolac vinyl ester, wherein the polymer material is prepared by the process according to the invention. Advantageously, in the polymer material further additional components, such as fillers and / or fiber materials, in particular glass fibers and / or glass fleeces and / or synthetic nonwovens, embedded, which give the material its strength.

The polymer material is preferably resistant to media in which chlorine or chlorine-containing compounds are present in the liquid or gaseous state, in particular to chlorine gas, bleach, anolyte, chlorine exhaust, moist chlorine and brine condensate resistant. The terminology corresponds to those known to the person skilled in the art from the chlor-alkali electrolysis technology. By anolyte is meant, for example, brine with free chlorine gas. Brine condensate is understood as meaning a brine solution which also contains chlorine. In particular, meets the

Polymer material meets this criterion at temperatures> 60 ° C. In this context, chlorine-containing compounds in this disclosure are understood as meaning compounds of the formula R-Cl-X, where R is an arbitrary reaction partner and X is the number of chlorine atoms.

Furthermore, the present invention claims means for receiving and / or transporting alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are contained, comprising the polymer material according to the invention. Optionally, this is a pipe or a container, wherein preferably a tube type E or D is used. With tube type E the mass content of the glass is maximally 40% and evenly distributed over the circumference. The inner layer of this tube type consists of a C-glass fiber reinforced resin layer of approximately 0.4 mm thickness. The outer layer consists of a layer of C-glass or synthetic fleece and a weather-resistant resin layer of maximum 0.2 mm thickness. The pipe type D is replaced by a

Chemistry protection layer of at least 2.5 mm thickness and a laminate structure characterized. The chemical protection layer is a resin-rich inner layer of at least 2.5 mm thickness. It consists of a C-glass non-woven reinforced

Reinharzschicht and includes in the further structure textile glass mats made of e-glass. The mass content of the glass in the chemical protective layer is between 25 and 30% and increases from the inside to the outside. The mass content in the bearing

Laminate construction is 60 ± 5% and consists of textile glass fabric, textile glass mats and / or textile glass rovings made of e-glass. The outer layer consists of a layer C Glass or synthetic fleece and a weather-resistant resin layer of maximum 0.2 mm thickness. This information is all known and accessible to the person skilled in the art, as stipulated in DIN 16 965 for pipes.

Advantageously, the pipe class to be used advantageously is the pipe class PX or PW, wherein in the pipe class PW on glass fleeces and / or synthetic nonwovens in the range, with the alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state of aggregation, come into contact, is omitted. It has been found that such glass webs leach under load with alkaline media such as chlorine gas, bleach, anolyte, chlorine exhaust air, humid chlorine and brine condensate and lead to clogging of the pipes. The designations of the pipe classes PX or PW are familiar to the person skilled in the art. The pipe class PX is designed for a temperature up to and including 80 ° C, whereas the pipe class PW is designed for a temperature up to and including 95 ° C. In a preferred embodiment of the invention, the means for receiving and / or transport of alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are contained via a filler comprising the ingredients of the curable composition of the invention based on the carrier Combine pyrogenic silica.

Advantageously, the invention finds above all use in

Apparatus of processes in which alkaline media in which chlorine or chlorine-containing compounds in the liquid or gaseous state are supplied and / or used. Preferably, the invention finds use in devices and / or in piping and / or container construction of a chlorine plant, in the alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

Physical state are produced and / or supplied.

In a further possible use of the polymer material according to the invention, the devices are devices of an electrolysis process by alkaline media in which chlorine or chlorine-containing compounds are prepared in liquid or gaseous state and / or supplied. The invention will be explained in detail below by way of example with reference to two exemplary embodiments. These examples include studies on removal rates of polymer materials flowed through by alkaline media containing chlorine or chlorine-containing compounds in the liquid or gaseous state.

A prior art tubing and tubing material of the present invention has been over a period of more than 4 years with an anolyte solution, i. flows through with brine loaded with free chorgas. The exact composition of the pipe materials is shown in the following table:

Table 1: Composition of the investigated pipe materials

At intervals of about one year, the tube thickness was determined at different measuring points (a total of 8 in number) and the resulting average determined. The results are shown in the tables below. Table 2: Removal rates at approximately 4 years of stress with an anolyte solution, ie with brine loaded with free chlorine gas, of

Polymer material according to the invention.

Table 3: Removal rates at approximately 4-year stress with an anolyte solution, i. with brine loaded with free chlorine gas of the polymer material of the prior art.

As can be seen from Tables 2 and 3 were removed over the period of about 4 years of the polymer material according to the prior art, an average of 2.2 mm, whereas only averaging 0.8 mm were removed in the polymer material according to the invention. This corresponds to a removal of 9% over 4 years for the polymer material according to the invention and a removal of 29% over 4 years for the polymer material according to the prior art. This could be with the composite material of the invention, a significant minimization the removal rate can be achieved by using the polymer material according to the invention.

In a further experiment, a tube type E of the

Pipe class PW used, the composition of the investigated

Pipe materials is shown in Table 4. Above all, different resins were used as a basis.

Table 4: Composition of the investigated pipe materials

A = resins, B = catalyst, C = accelerator, D = hardener, E = retarder, stabilizer, G = paraffin, H = solvent UV protection in all pipelines Tinuvin ^® 5050 ^® from Ciba was used, and as wax throughout BYK-S 750 of Atlana group was used.

Also in this long-term trial over 4 years was by the

Pipes (sample 1 - 13) passed an anolyte solution and measured the removal over time. The result is shown in FIG. The unshaded bars indicate the average removal rate in mm over a period of 4 years, while the shaded bars indicate the maximum removal rate, which was determined by determining a single value. It is striking that sample 7, which corresponds to the composition according to the invention in a metal-poor formulation, has by far the lowest removal rate. The metal-free formulation reflects sample 12, which gives somewhat better results than sample 13, which is based on the same resin but has a prior art formulation. Sample 12 also gives comparable results to Sample 11, which also

Cobalt concentrations in the usual prior art concentrations. These experiments clearly show that it is important to fine-tune the composition in order to generate a polymer material which has a low removal rate and additionally has even reduced to no metals.

Advantages resulting from the invention: - Polymer material with good resistance to alkaline media containing chlorine or chlorine-containing compounds in the liquid or gaseous state, in which the removal rate is reduced over time.

Polymer material is resistant even at high temperatures in the presence of alkaline media containing chlorine or chlorine-containing compounds in the liquid or gaseous state

Polymer material has extended life by reducing erosion

The blockage of corresponding piping through

Ablation products is reduced by a lower removal rate. All ingredients of the curable composition are available worldwide

Claims

claims

1. comprising curable composition

a resin in the form of epoxy novolac vinyl ester, wherein the resin is contained in a concentration of 96.3 to 98.95%,

a catalyst wherein the catalyst is in the form of a 6%

Cobalt solution is contained in a concentration of 0.05 to 0.1%, an accelerator, wherein the accelerator is contained in the form of dimethylaniline in a concentration of 0 to 0.1%, a curing agent, wherein the curing agent in the form of cumene hydroperoxide in contained in a concentration of 1 to 2%,

Paraffin, the paraffin being in the form of wax in a concentration of 0 to 1%.,

and the concentration data to 100% of a to be cured

Refer to total mass.

2. comprising curable composition

a resin in the form of epoxy novolac vinyl ester, wherein the resin in a

Concentration of 94 to 97.95% is included

an accelerator, the accelerator being in the form of N, N-

Dimethylaniline is contained in a concentration of 0.05 to 0.2%, a curing agent, wherein the curing agent in the form of dibenzoyl peroxide in a

Concentration of 2 to 4% is included

a retarder, wherein the retarder is in the form of p-tert

Butylcatechol in a concentration of 0 to 0.3% is a UV stabilizer, wherein the UV stabilizer is contained in a concentration of 0 to 0.5%,

Paraffin, wherein the paraffin is contained in the form of wax in a concentration of 0 to 1%,

and the concentration data to 100% of a to be cured

Refer to total mass.

3. A method for producing a polymer material comprising the curable composition according to any one of claims 1 or 2, comprising the following steps a. Resin and catalyst are subjected to pre-acceleration for a period not exceeding the expiration date of the resin,

b. the accelerator, hardener, retarder, UV stabilizer are added in the order given, and a hardenable mass is generated,

e. optionally paraffin is applied to the workpiece from the outside, and f. The workpiece is subjected to a heat treatment for 8 hours at 80 ° C and a finished polymer material is generated.

4. A method for producing a polymeric material according to claim 3, characterized in that in the curable composition further additional

Components, such as fillers and / or fiber materials, in particular

Glass fibers and / or glass fleeces and / or synthetic nonwovens are embedded.

5. Polymer material comprising the ingredients of the curable composition according to any one of claims 1 or 2 based on the resin epoxy novolac vinyl ester, wherein the Polymerkwerkstoff is prepared by a method according to claim 3.

6. Polymer material according to claim 5, characterized in that further additional components, such as fillers and / or fiber materials, in particular glass fibers and / or glass fleeces and / or synthetic nonwovens, are embedded in the polymer material.

7. Polymer material according to one of claims 5 or 6, characterized

in that the polymer material is resistant to alkaline media in which chlorine or chlorine-containing compounds are present in liquid or gaseous state, in particular with respect to chlorine gas,

Bleach, anolyte, Chlorabluft, wet chlorine and brine condensate is resistant.

8. Polymer material according to claim 7, characterized in that the

Composite is resistant at temperatures> 60 ° C.

9. means for receiving and / or transporting alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

Physical state are included, comprising the polymer material according to claim 5.

10. means for receiving and / or transport of alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

State of aggregation contained according to claim 9, characterized in that it is a tube.

1 1. Means for receiving and / or transporting alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

State of aggregation contained according to claim 10, characterized in that it is a tube type E or D.

12. means for receiving and / or transport of alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

State of aggregation contained according to claim 11, characterized in that it is a pipe class PX or PW, wherein in the

Pipe class PW on glass fleeces and / or synthetic nonwovens in the area which comes into contact with the alkaline media in which chlorine or chlorine-containing compounds in the liquid or gaseous state are in contact, is omitted.

13. means for receiving and / or transport of alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

State of aggregation contained according to claim 9, characterized in that it is a container.

14. means for receiving and / or transporting alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous

State of aggregation are contained according to one of claims 9 to 13, characterized in that the agents can be connected to one another via a filler comprising the ingredients according to one of claims 1 or 2 based on the carrier pyrogenic silica.

15. Use of the polymer material according to claim 5 in apparatuses of processes in which alkaline media in which chlorine or chlorine-containing compounds in the liquid or gaseous state are fed and / or used.

16. Use of the polymer material according to claim 5 in devices

and / or in piping and / or tank construction of a chlorine plant in which alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are produced and / or supplied.

Use of the composite according to claim 5, wherein the devices are devices of an electrolysis process, in which alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are produced and / or supplied.